Benzotriazole UV absorbers having enhanced durability

ABSTRACT

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings. This is particularly the case when the 3-position of the phenyl ring is also substituted by phenyl or phenylalkyl such as α-cumyl. Compounds where the 5-position of the benzo ring are substituted by perfluoroalkyl such as trifluoromethyl are particularly of interest for both their enhanced durability and for their excellent solubility and excellent color properties in some thermoplastic compositions when the phenyl ring is substituted at the 3-position by hydrogen or tert-alkyl.

[0001] This is a continuation-in-part of application Ser. No.08/961,127, filed on Oct. 30, 1997, which application claims the benefitunder 35 USC 119(e) of U.S. application Ser. No. 08/745,146, filed onNov. 7, 1996, and converted into a Provisional Application by petitionunder 37 CFR 1.53(b)(2)(ii), filed on May 23, 1997, and granted on Aug.7, 1997.

[0002] Benzotriazole UV absorbers being substituted in the benzo ring byelectron withdrawing moieties exhibit enhanced durability and low lossrates when incorporated into automotive coatings and thermoplasticcompositions.

BACKGROUND OF THE INVENTION

[0003] The benzotriazoles have long been an important class of UVabsorbers and have gained wide commercial importance and acceptance formany industrial applications. The prior art is replete with referencesto their manufacture and utility. However, as requirements become evermore stringent and demanding, the search for still more stable anddurable benzotriazoles continues. The gradual phase out of HAPSsolvents, such as xylene, because of environmental concerns and theirreplacement with non-HAPS solvents, such as esters, ethers or ketones,and increased durability requirements for automotive coatings make thissearch more urgent. Indeed, the automotive industry is most concernedabout UVA losses from automotive paints and coatings as seen in thepublication by J. L. Gerlock et al., Proc. 36th Annual Tech. Sym.(Cleveland Coating Society), May 18, 1993.

[0004] Vysokomol Soedin, Ser. A, 18(3), 553 (1976) describes the lineardependence of hydrogen bond strength and photostability inbenzotriazoles.

[0005] J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995)describe the photodegradation of benzotriazole UV absorbers inpoly(methyl methacrylate) films. Structural variation generally causedonly small differences in the rates of degradation unless thesubstitution disrupted the intramolecular hydrogen bonds which arecritical for stability. Pickett et al. did not test any benzotriazolescontaining both electron withdrawing and electron donating groups as inthe instant invention.

[0006] J. Catalan et al., J. Am. Chem. Soc., 114, 964 (1992) and H. J.Heller, Eur. Polymer J. Suppl. 1969, 105 both suggest that a bulkysubstituent such as tert-butyl ortho to the hydroxy group on the phenylring will increase stability in highly polar systems.

[0007] The prior art leads one to the conclusion that strengthening thehydrogen bond leads to a more stable benzotriazole, but does not teachhow this can be accomplished. The instant invention disclosesbenzotriazoles which exhibit enhanced durability, but surprisingly thisenhanced durability is not always related to greater hydrogen bondstrength. Indeed, compounds with enhanced durability often have weaker,not stronger hydrogen bonds.

[0008] U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004;4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 describeselected benzotriazoles, substituted in the 3-position of thehydroxyphenyl ring by an α-cumyl group, which show very good durabilityin automotive coatings. These benzotriazoles represent the present stateof the art. The instant invention is directed at preparingbenzotriazoles which exhibit still better durability and low loss ratesfrom the prior art benzotriazoles.

[0009] U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914describe red-shifted benzotriazoles. These benzotriazoles aresubstituted in the 3-position of the phenyl ring with an α-cumyl groupand at the 5-position of the benzo ring by thio ethers, alkylsulfonyl orphenylsulfonyl moieties. Red-shifting the benzotriazoles is desirablefor spectral reasons. A group at the 5-position which is also electronwithdrawing provides additional benefits in low loss rates anddurability as found in the instant invention. Missing from these patentsare any alkylsulfones with seven or fewer carbon atoms. When suchsulfonyl substituents are combined with specifically α-cumyl moieties,extremely durable compounds result which, due to the bulk of the α-cumylmoiety have sufficiently low volatility to be useful in coating andother polymer systems.

[0010] The presence of an α-cumyl or phenyl group ortho to the hydroxygroup on the phenyl ring exerts a surprisingly large positive effect onbenzotriazole photostability in coatings and photographic gel systems.The magnitude of this effect, particularly when compared to a tert-butylgroup in that position, is well beyond prediction. The combination ofboth an electron withdrawing group on the benzo ring and an α-cumyl orphenyl group on the phenyl ring in the same molecule leads to extremelydesirable properties in coating systems when high UV absorber permanenceis critical.

[0011] Novel compounds meeting these parameters as being extremelystable in aggressive use environments constitute a first portion of thisinvention.

[0012] The presence of the electron withdrawing moiety at the 5-positionof the benzo ring has a powerful stabilizing effect on benzotriazoles ingeneral and is observed in other polymer systems such as polycarbonateand poly(vinyl chloride) substrates as well. However, the effect ofhaving an α-cumyl or phenyl group ortho to the hydroxy moiety on thephenyl ring is much smaller to non-existent in some polymer systems suchas polycarbonate or poly(vinyl chloride) even though critical forcoating systems as described above.

[0013] In addition to being more photostable, the compounds of thisinvention are red-shifted, absorbing strongly in the 350-400 nmwavelength range. While such red-shifting is desirable in that a greaterportion of the UV spectrum is absorbed, this can also introduce color ifthe absorption beyond 400 nm is significant. This can limit the use ofsuch compounds, particularly in systems such as polycarbonate glazingapplications or present difficulties in various pigmented systems.

[0014] It is found that the nature of the substituent ortho to thehydroxyl group on the phenyl ring has an unexpected impact on colorimparted to the substrate by the benzotriazole. Thus, relatively subtledifferences in substitution on the phenyl ring can have a large impacton the resulting color and the applicability of the benzotriazole inspecific color sensitive applications. There are striking differencesbetween having hydrogen, alkyl or α-cumyl at this 3-position.

[0015] Furthermore, it is found that, when the 5-position of the benzoring is substituted with a trifluoromethyl group, the resultingbenzotriazole not only exhibits the same or greater enhanced stabilitywhen incorporated into thermoplastic resins, but also imparts less colorthan related benzotriazoles substituted at the 5-position with otherelectron withdrawing moieties such as sulfonyl or carbonyl. Thesetrifluoromethyl compounds also absorb strongly in the 350-400 nmwavelength range despite the low color and are extremely compatible in awide range of substrates such as acrylic resins, hydrocarbons,polycarbonates and poly(vinyl chloride).

[0016] There are a multitude of general references to benzotriazoleshaving in the 5-position of the benzo ring electron withdrawing groupssuch as esters, amides, sulfones and the like that are not substitutedin the 3-position of the phenyl ring by an α-cumyl or phenyl moiety. Inmany of these references the broadly described compounds areunexemplified and no teaching or appreciation taught of the positiveeffect on photostability described in this invention. In any event, thevast majority of these structures fall well outside the scope of instantinvention. Perfluoroalkyl, specifically trifluoromethyl, is an idealsubstituent for the 5-position of the benzo ring. The prior art relevantto this substituent is very limited and exemplifies none of the instantcompounds. As a result, said prior art naturally fails to point out theimportant advantages regarding stability, color and compatibilityachievable with the 5-trifluoromethyl substituted benzotriazoles of thisinvention. The general, unexemplified references to alkyl substitutedwith halogen are acknowledged, but are clearly irrelevant to the instantinvention.

[0017] German Offen. 1,670,951 describes inter alia the use of methylene(or alkylidene) bis-benzotriazoles substituted with electron withdrawinggroups in polymeric resins. Especially useful are the asymmetricalcompounds where only one benzotriazole moiety is substituted. Suchasymmetric compounds have considerably less color.

[0018] German 116,320 provides a method of preparing benzotriazoleN-oxide intermediates which can be converted into dyes and lightstabilizers. The N-oxide of5-trifluoromethyl-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole isdisclosed This N-oxide could be reduced to the correspondingbenzotriazole which is substituted at the 5-position of the phenyl ring.However, this benzotriazole is clearly outside the scope of the instantclaims. Other related light stabilizer intermediates are genericallydisclosed in this reference, but none where ever converted to actualbenzotriazole UV absorbers. The outstanding properties of suchbenzotriazole UV absorbers clearly went undiscovered.

[0019] Japanese Hei 3-57690 claims a color developer sheet compositionscontaining salicylic acid salts and benzotriazoles. Broadly describedare benzotriazoles which may be substituted on the benzo ring withunspecified trihalomethyl. However, other benzotriazole ringsubstituents also are broadly described to include unspecified alkyl,alkoxy, aryloxy, amino, cyano, acyl, nitro and halogen. The onlybenzotriazoles named as typical examples are either unsubstituted on thebenzo ring or substituted by chlorine. The preference is for liquidcompounds. The 3-position of the phenyl ring is specified as tert-alkyl.While this reference broadly discloses a wide variety of benzotriazolederivatives in its photographic compositions many are electron donatingand produce compounds which are in photostability inferior not only tothe instant compounds, but also to standard unsubstitutedbenzotriazoles. No examples or differentiation between within thisdiverse array is seen. Further, while generic trihalomethyl isdescribed, no compounds of this description are shown or furtherdescribed in any way. Additionally, trichloro, tribromo and triiodocompounds are clearly outside the scope of the instant invention.

[0020] Japanese Sho 47-15210 describes resin compositions containingselected benzotriazoles substituted by a fluorinated alkyl. The genericstructures allows for a fluorinated alkyl, but not necessarilyperfluorinated alkyl, to be added to either or both the benzo or phenylrings at any position (the substituents are floating in the generialformula). Non-fluorinated substituents, one on each ring, are defined ashydrogen, halogen, hydroxy, alkyl and alkoxy with no other more specificdescription. The exemplified resins are poly(vinyl chloride),polycarbonate, ABS and nylon. Seven compounds are specificallyexemplified all outside the scope of the instant invention plus onecomposition containing 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole. Nophysical data or synthesis for any of these seven compounds are given.

[0021] The seven compounds exemplified in the Japanese reference aregiven below:

[0022] a. 2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

[0023] b.5-methyl-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

[0024] c.5-methoxy-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole;

[0025] d.5-chloro-2-(2-hydroxy-4-trifluoromethylphenyl)2H-benzotriazole;

[0026] e. 5-peroxymethoxy-2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole;

[0027] f.5-perfluorooctyl-2-(2-hydroxy-4-methylphenyl)-2H-benzotriazole; and

[0028] g.5-perfluorooctyl-2-(2-hydroxy-4-trifluoromethylphenyl)-2H-benzotriazole.

[0029] There are several distinct differences between the disclosure ofthis Japanese reference and the instant invention. First all theexemplified compounds of the Japanese reference are substituted in the4-position of the phenyl ring by groups other than hydrogen. Thereference allows for substitution of either fluoroalkyl or fluoroalkoxyon any site on either ring as a means of providing for an improved UVabsorber. Data given in this application shows this teaching to beinaccurate. Electron withdrawing moities on the phenyl ring as found ina, b, c, d, and g above, are shown to provide compounds with lessdurability than unsubstituted derivatives as seen in Example 77.Spectral coverage in the red region is also compromised as seen inExample 74. Significantly,2-(2-hydroxy-5-trifluoromethylphenyl)-2H-benzotriazole which is verysimilar to compound a above, is blue-shifted relative to benzotriazolessuch as 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole as seen in Example74. Blue-shifting is undesirable since the need for coverage in the350-400 nm region is critical for UV absorbers.

[0030] An electron donating group at the 5-position of the benzo ringsuch as the ether compound c above reduces stability as seen in Example77. While the Japanese reference states fluoroalkyl or fluoroalkoxyradical leads to enhanced stability under light, the instant inventionshows that it is the electron withdrawing nature of the group at the5-position on the benzo ring that confers greater photostability. Nosuch inference in seen in the Japanese reference, and the electrondonating ether even a fluorinated ether is counterindicated for enhancedstability.

[0031] Furthermore, all examples in the Japanese reference bear only onesubstituent on the phenyl ring and that is specifically at the4-position. The instant invention specifically claims only hydrogen atthe 4-position as substitution at the 4position brings undesirableconsequences for the use of these compounds in many applications. Thecompound f is the closest to the instant invention, but it issubstituted by a 4-methyl group. As seen in Example 79, substitution ofthe phenyl ring by an electron donating group at the 5-positiondiminishes photostability in coatings. Pickett et al. report the sameloss of durability for such compounds in thermoplastics. The electrondonating characteristics of methyl are less pronounced, but are stillsimilar to alkoxy. The σ_(p) value, as measure of the electronic effectof substituents for aromatic methoxy substitution is −0.27 while formethyl is −0.17 (March J. “Advanced Organic Chemistry”, 2nd Ed. (1977),McGraw-Hill, New York, p 253).

[0032] While the generic disclosure of the Japanese reference overlapsformula I of the instant application no such compound is specificallydisclosed in the Japanese reference. As mentioned above, all examples ofthe Japanese reference are substituted at the 4-position of the phenylring, most contain the electron withdrawing CF₃ group at the 4-position.Compounds of the instant invention explicitly denote hydrogen at the4-position of the phenyl ring for reasons including color and stability,and expressly designate the 5-position of the benzo ring as the locationof the perfluoroalkyl moiety for reasons of stability and spectralcoverage.

[0033] U.S. Pat. Nos. 3,936,305; 4,681,905; 4,684,679; 4,684,680 and5,108,835 teach the2,2′-methylene-bis[4-hydrocarbyl-6-(benzotriazol-2-yl)phenols] havinghigh molar activities and low volatility. In addition U.S. Pat. Nos.5,292,890 and 5,360,850 teach that asymmetrical bis-benzotriazolesdisplay higher solubility in organic non-polar solvents that thesymmetrical dimers made from the same benzotriazole monomer.

[0034] U.S. Pat. No. 5,166,366 describes a process for making2,2′-methylene-bis[6-(benzotriazol-2-yl)-4-hydrocarbylphenol] or5,5′-methylene-bis(2-hydroxy-4alkoxybenzophenone) usingbis(dialkylamino)methane.

[0035] Related bis-benzotriazoles of the instant invention substitutedat one or at both of the benzotriazole rings by perfluoroalkyl areunknown and provide the same improvement to these bis-benzotriazoles asmentioned above, namely enhanced durability and broader spectralcoverage. Substitution of only one of the benzotriazole moieties inthese bis-benzotriazoles by perfluoroalkyl gives the additionaladvantage of much lower color than the disubstituted compound, indeednearly to the color of the bis-benzotriazole not substituted byperfluoroalkyl.

DETAILS OF THE DISCLOSURE

[0036] The instant invention pertains to novel benzotriazole UVabsorbers having enhanced stability and durability and a low loss ratewhen incorporated into automotive coatings. These new benzotriazole UVabsorbers are also soluble in a variety of substrates includingthermoplastic polymers and often are essentially colorless even thoughabsorbing in the 350-390 nm range.

[0037] More specifically, the instant invention pertains to newbenzotriazole compounds of formula I, II, III or IV

[0038] wherein

[0039] G₁ is hydrogen or chloro,

[0040] G₂ is cyano, perfluoroalkyl of 1 to 12 carbon atoms, fluoro,—CO—G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO— or E₃SO₂—,

[0041] G₃ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

[0042] G₆ is perfluoroalkyl of 1 to 12 carbon atoms,

[0043] G₇ is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,

[0044] E₁ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1to 24 carbon atoms substituted by one or two hydroxy groups,

[0045] E₂ and E₂′ are independently straight or branched alkyl chain of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted onthe phenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E₂ andE₂′ are independently said alkyl of 1 to 24 carbon atoms or said alkenylof 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁, —OE₄,—NCO, —NH₂,—NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylor said alkenyl interrupted by one or more —O—, —NH— or —NE₄— groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, —OE₄ or —NH₂ groups or mixtures thereof;

[0046] n is 1 or 2,

[0047] when n is 1, E₅ is Cl, OE₆ or NE₇E₈, or

[0048] E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or —OCO—E₁₁, or straight or branchedchain C₁-C₂₄alkyl which is interrupted by —O—, —S— or —NE₁₁ and whichcan be unsubstituted or substituted by —OH or —OCO—E₁₁, C₅-C₁₂cycloalkyl which is unsubstituted or substituted by —OH, straight chainor branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —OH,C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl,

[0049] E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which isunsubstituted or substituted by one or more OH, OE₄ or NH₂ groups, or—OE₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 andE₂₁ is alkyl of 1 to 12 carbon atoms,

[0050] E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring, or

[0051] E₅ is —X—(Z)_(p)—Y—E₁₅

[0052] wherein

[0053] X is —O— or —N(E₁₆)—,

[0054] Y is —O— or —N(E₁₇)—,

[0055] Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

[0056] m is zero, 1 or 2,

[0057] p is 1, or p is also zero when X and Y are —N(E₁₆)— and —N(E₁₇)—,respectively,

[0058] E₁₅ is a group —CO—C(E1 ₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, formstogether with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen ormethyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula

[0059] wherein the symbols E₁, G₂, X, Z, m and p have the meaningsdefined above, and E₁₆ and E₁₇ independently of one another arehydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms,or is cyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the casewhere Z is ethylene, also forms ethylene,

[0060] when n is 2, E₅ is one of divalent radicals —O—E₉—O— or—N(E₁₁)—E₁₀—N(E₁₁)—,

[0061] E₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene,cyclohexylene, straight or branched chain C₄-C₁₀alkylene which isinterrupted by —O— or by —CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—,

[0062] E₁₀ being straight or branched chain C₂-C₁₂alkylene which may beinterrupted by —O—, cyclohexylene, or

[0063] or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazinering,

[0064] E₁₄ is straight or branched chain C₂-C₈alkylene, straight orbranched chain C₄-C₁₀alkylene which is interrupted by —O—,cycloalkylene, arylene or

[0065] where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18carbon atoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene,

[0066] E₁₁ is hydrogen, straight or branched chain C₁-C₁₈alkyl,C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl, C₆-C₁₄arylor C₇-C₁₅aralkyl,

[0067] E₁₂ is straight or branched chain C₁-C₁₈alkyl, straight orbranched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl, C₆-C₁₆aryl orC₇-C₅aralkyl,

[0068] E₁₃ is H, straight chain or branched C₁-C₁₈alkyl which issubstituted by —PO(OR₁₂)₂, phenyl which is unsubstituted or substitutedby OH, C₇-C₁₅aralkyl or —CH₂O E₁₂,

[0069] E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one or two alkyl of 1 to 4carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where theperfluoroalkyl moiety is of 6 to 16 carbon atoms,

[0070] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylyleneor cycloalkylidene, and

[0071] T is —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—CO—,—CO—CH₂—CO—, —CO—E—CO—, —COO—E—OCO— or —CO—NG₅—E—NG₅—CO—,

[0072] where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5to 12 carbon atoms, or alkylene interrupted or terminated bycyclohexylene of 8 to 12 carbon atoms;

[0073] G₅ is G₃ or hydrogen, and

[0074] with the proviso that when T is —SO—, —SO2—, —SO—E—SO— or—SO₂—E—SO₂—, E₁ is not hydrogen, straight or branched chain alkyl of 1to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of7 to 15 carbon atoms; or when E₃ is alkyl of 1 to 6 carbon atoms, E₁ isnot hydrogen or phenyl, and the sum of E₁ plus E₂ is equal to or greaterthan 8; and when E₃ is alkyl of 8 to 18 carbon atoms or alkenyl of 2 to24 carbon atoms, E₁ is not hydrogen, straight or branched chain of 1 to24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7to 15 carbon atoms; or when G₂ is cyano, —CO—G₃. —CONHG₃, —CON(G₃)₂ or—COOG₃, then E₁ is phenyl or phenylalkyl of 7 to 15 carbon atoms, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms; or when E₁ is hydrogen, E₂ is not methyl.

[0075] Preferably, the new benzotriazole is a compound of formula I

[0076] wherein

[0077] G₁ is hydrogen,

[0078] G₂ is cyano, CF₃—, fluoro, —CO—G₃ or E₃SO₂—,

[0079] G₃ is straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms,

[0080] E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenylor said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1to 4 carbon atoms,

[0081] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —OE₄, —NCO, —NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixturesthereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH— or —NE4— groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —OE₄ or —NH₂ groups or mixturesthereof;

[0082] E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10carbon atoms or said aryl substituted by one or two alkyl of 1 to 4carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where theperfluoroalkyl moiety is of 6 to 16 carbon atoms; or

[0083] is a compound of formula I wherein,

[0084] G₁ is hydrogen,

[0085] G₂ is CF₃—, fluoro or E₃SO₂—,

[0086] E₁ is hydrogen or straight or branched alkyl of 4 to 24 carbonatoms,

[0087] E₂ is as defined above, and

[0088] E₃ is straight or branched chain alkyl of 1 to 7 carbon atoms,

[0089] with the proviso that the sum of the carbon atoms in E₁ and E₂ isgreater than or equal to 8 when G₂ is E₃SO₂.

[0090] Preferably, the benzotriazole is also a compound of formula IIIA

[0091] wherein

[0092] G₁ is hydrogen,

[0093] G₂ is is CF₃— or fluoro,

[0094] E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms,

[0095] E₅ is —OE₆ or —NE₇E₈, or

[0096] E₅ is

—X—(Z)_(p)—Y—E₁₅

[0097] wherein

[0098] X is —O— or —N(E₁₆)—,

[0099] Y is —O— or —N(E₁₇)—,

[0100] Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to threenitrogen atoms, oxygen atoms or a mixture thereof, or isC₃-C₁₂-alkylene, butenylene, butynylene, cyclohexylene or phenylene,each substituted by a hydroxyl group,

[0101] m is 0, 1, 2 or 3,

[0102] p is 1, or p is also zero when X and Y are —N(E₁6)— and —N(E₁₇)—,respectively,

[0103] E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, formstogether with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ is hydrogen ormethyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ ishydrogen, C₁-C₁₂-alkyl or a group of the formula.

[0104] Preferably, the benzotriazole is also a compound of formula IV

[0105] wherein

[0106] G₆ is CF₃,

[0107] G₇ is hydrogen or CF₃,

[0108] E₂ and E₂′ are independently straight or branched alkyl chain of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted onthe phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

[0109] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylyleneor cycloalkylidene.

[0110] Most preferably, the new benzotriazole is a compound of formula I

[0111] wherein

[0112] G₁ is hydrogen,

[0113] G₂ is CF₃—,

[0114] E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenylor said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1to 4 carbon atoms,

[0115] E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; or E₂ is said alkyl of 1 to 24 carbonatoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more—OH, —OCOE₁₁, —NH₂ or —NHCOE₁₁, or mixtures thereof; or said alkyl orsaid alkenyl interrupted by one or more —O— which can be unsubstitutedor substituted by one or more —OH groups; or

[0116] is a compound of formula I wherein,

[0117] G₁ is hydrogen,

[0118] G₂ is CF₃—,

[0119] E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms, and

[0120] E₂ is as defined above.

[0121] Most preferably, the benzotriazole is also a compound of formulaIIIA

[0122] wherein

[0123] G₁ is hydrogen,

[0124] G₂ is CF₃—,

[0125] E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbonatoms or phenylalkyl of 7 to 15 carbon atoms,

[0126] E₅ is —OE₆ or —NE₇E₈ where

[0127] E₆ is hydrogen, straight or branched chain C₁-C₂ ₄alkyl which isunsubstituted or substituted by one or more OH groups, or —OE₆ is—(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ isalkyl of 1 to 12 carbon atoms, and

[0128] E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by—O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl,or E₇ and E₈ together with the N atom are a pyrrolidine, piperidine,piperazine or morpholine ring.

[0129] Most preferably, the benzotriazole is also a compound of formulaIV

[0130] wherein

[0131] G₆ is CF₃,

[0132] G₇ is hydrogen or CF₃,

[0133] E₂ and E₂′ are independently straight or branched alkyl chain of1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted onthe phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

[0134] L is methylene.

[0135] Compounds which are especially preferred are:

[0136] (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzo-triazole;

[0137] (b)5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

[0138] (c)5-trifluoromethyl-2-(2-hydroxy-3,5di-tert-octylphenyl)-2H-benzotriazole;

[0139] (d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octyl-phenol];

[0140] (e)methylene-2-[4-tert-octyl-6(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];

[0141] (f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamicacid;

[0142] (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0143] (h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;

[0144] (i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

[0145] (j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzo-triazole;

[0146] (k)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;

[0147] (l)5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzo-triazole;

[0148] (m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;

[0149] (n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzo-triazole;

[0150] (o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;

[0151] (p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

[0152] (q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

[0153] (r)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole;

[0154] (s)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;

[0155] (t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

[0156] (u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;

[0157] (v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

[0158] (w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

[0159] (x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0160] (y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0161] (z)5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole;

[0162] (aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;and

[0163] (bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole.

[0164] Examples of these various radicals are as follow:

[0165] When any of E₁ to E₂₁ is alkyl, such groups are, for example,methyl, ethyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,tert-amyl, 2-ethylhexyl, tert-octyl, lauryl, tert-dodecyl, -tridecyl,n-hexadecyl, n-octadecyl and eicosyl; when any of said radicals isalkenyl, such groups are, for example, allyl or oleyl; when any of saidradicals is cycloalkyl, such groups are, for example, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl; when any of saidradicals are phenylalkyl, such groups are, for example, benzyl,phenethyl, α-methylbenzyl and α,α-dimethylbenzyl; and when any of saidradicals is aryl, they are, for example, phenyl, naphthyl, or whensubstituted by alkyl are, for example, tolyl and xylyl. When E₆ is alkylsubstituted by one or more —O— groups and/or substituted by one or more—OH, the —OE₆ moiety can be —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ wherew is 1 to 12 and E₂₁, is alkyl of 1 to 12 carbon atoms, for example.

[0166] When E is alkylene, it is, for example, ethylene, tetramethylene,hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene,octamethylene, decamethylene and dodecamethylene; when E iscycloalkylene, it is, for example, cyclopentylene, cyclohexylene,cycloheptylene, cyclooctylene and cyclododecylene; and when E isalkylene interrupted or terminated by cyclohexylene, it is, for example,the saturated diyl radical derived from limonene, herein calleddihydrolimonenediyl.

[0167] When E is alkylene, it is, for example, ethylene, tetramethylene,hexamethylene, 2-methyl-1,4-tetramethylene, hexamethylene,octamethylene, decamethylene and dodecamethylene; when E iscycloalkylene, it is, for example, cyclopentylene, cyclohexylene,cycloheptylene, cyclooctylene and cyclododecylene; and when E isalkylene interrupted or terminated by cyclohexylene, it is, for example,the saturated diyl radical derived from limonene, herein calleddihydrolimonenediyl.

[0168] When the instant compounds contain a free carboxyl moiety whereE₂ is —CH₂CH₂COOE₆ where E₆ is hydrogen, the alkali metal or amine saltsof said acids are also contemplated as part of this invention allowingsuch UV absorbers to be used in aqueous systems due to the enhancedwater solubility of such instant compounds.

[0169] E₆, E₇ and E₈ can be the following C₃-C₁₈alkyl radicals which areinterrupted by —O—, —S—, or —NE₁₁— and can be substituted by OH:methoxyethyl, ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl,CH₃OCH₂CH₂OCH₂CH₂—, CH₃CH₂OCH₂CH₂OCH₂CH₂—, C₄H₉OCH₂CH₂OCH₂CH₂—,ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl,2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, —CH₂CH₂—NH—C₄H₉,—CH₂CH₂CH₂NH—C₈H₁₇ and —CH₂CH₂CH₂—N(CH₃)—CH₂CH(C₂H₅)C₄H₉,

[0170] E₆, E₇, E₈, E₁₁, and E₁₂ can be the following C₅-C₁₂cycloalkylradicals: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl orcyclodecyl. In the case of E₆, the radical can also be substituted by—OH.

[0171] E₇, E₈ and E₁₁ can be the following alkenyl radicals: allyl,methallyl, 2-n-hexenyl or 4-n-octenyl.

[0172] When E₆ is alkenyl, it can have the same meaning as E₇, E₈ andE₁₁ as alkenyl radicals, but it can also be —CH═CH₂, n-undec-10-enyl orn-octadec-9-enyl, and it is also possible for the radical E₆ to besubstituted by —OH.

[0173] E₇ and E₈ can be the following C₇-C₁₅aralkyl radicals: benzyl,a-phenethyl, 2-phenethyl or 4-tert-butylbenzyl.

[0174] When E₁₁, E₁₃ or E₁₂ are aralkyl, they can, independently of oneanother, have the same meaning as E₇ or E₈.

[0175] Independently of one another, E₇, E₈ and E₁₁ can be the followingC₆-C₁₄ aryl radicals: phenyl, α-naphthyl or β-naphthyl.

[0176] When E₇ and E₈ are C₁-C₃ hydroxyalkyl, they can be the followingradicals: hydroxymethyl, 2-hydroxyethyl or 2-hydroxypropyl.

[0177] As C₂-C₈ alkylene, E₉ and E₁₄ can be the following radicals:ethylene, propylene, butylene, hexylene or octylene.

[0178] As alkylene, E₁₀ can be the same radicals, but can, in addition,also be higher-molecular groups such as decylene or dodecylene.

[0179] When E₉ is a C₄-C₈alkenylene radical, the following is an exampleof a suitable group: butenylene.

[0180] In the case of E₉ and E₁₄, suitable straight or branched chainC₄₋₁₀alkylene groups which are interrupted by —O— are the followinggroups: —CH₂CH₂OCH₂CH₂—,—CH(CH₃)—CH₂—O—CH₂—CH(CH₃)—CH₂CH₂OCH₂CH₂OCH₂CH₂— and—CH₂CH₂OCH₂CH₂OCH₂CH₂OCH₂CH₂—.

[0181] When E₁₄ is a cycloalkylene radical, the following groups areembraced: 1,3-cyclohexylene and 1,4-cyclohexylene.

[0182] When E₁₄ is arylene, this can be, specifically, the followinggroups: 1,3-phenylene or 1,4-phenylene.

[0183] As C₂-C₁₂-alkylene, Z is a straight or branched chain. It is forexample: ethylene, propylene, tetramethylene, hexamethylene,octamethylene, dodecamethylene, 1,1-ethylidene, 2,2-propylidene,2,2-amylidene or 2-ethylhexamethylene. C₂-C₆-alkylene groups arepreferred

[0184] When Z is C₄-C₁₂-alkylene which is interrupted by oxygen, it isfor example: —CH₂—CH₂—O—CH—₂—CH₂—, —CH₂—CH₂—O—CH₂—CH₂—CH₂,CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂ or —CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—O—CH₂—CH₂—,and, when alkylene is interrupted by nitrogen, a group —N(E₁₆)— ismeant, where E₁₆ is as defined in the foregoing, for example—CH₂—CH₂—NH—CH₂—CH₂—CH₂—CH₂, —CH₂—CH₂—CH₂—NH—(CH₂)8— or—CH₂CH₂—CH₂—N(CH₃—CH₂—CH(C₂H₅)(CH₂)₄—.

[0185] As C₃-C₁₂-alkylene substituted by a hydroxyl group, Z is2-hydroxytetramethylene, 2-hydroxyhexamethylene and, in particular,2-hydroxytrimethylene.

[0186] As cyclohexylene, Z is for example 1,4-cyclohexylene and, inparticular, 1,2-cyclohexylene.

[0187] As phenylene, Z is for example m-phenylene or p-phenylene.

[0188] m can be zero, 1, 2 or 3, but it is preferably 2.

[0189] p is preferably 1, but can also be zero if both X and Y are boundby way of nitrogen.

[0190] As C₁-C₈-alkyl, E₁ is for example: methyl, ethyl, n-propyl,isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, tert-amyl, n-nexyl,n-heptyl, n-octyl, 2-ethylhexyl or tert-octyl. Tert-butyl is preferred

[0191] As C₁-C₁₂-alkyl, E₁₆, E₁₇ and E₂₀ can have the same meaning asthat given in the foregoing for R₁, and can additionally be straight orbranched-chain nonyl, decyl, undecyl, or dodecyl.

[0192] When E₁₆ and E₁₇ are alkyl interrupted by oxygen atoms, theexamples which apply are the same as those described in the foregoingfor Z.

[0193] Examples for E₁₆ and E₁₇ as aralkyl are: benzyl, α-methylbenzyl,1-phenylethyl, α,α-dimethylbenzyl or 1-phenylpropyl.

[0194] If Z is ethylene, E₁₆ and E₁₇ together can likewise formethylene, which is equivalent to a bridging over by way of a piperazinegroup.

[0195] When Y is a group —N(E₁₇)—, E₁₅ and E₁₃ together make up a group—CO—CH═CH—CO—, and thus form the substituent

[0196] on the group —X—(Z)_(p)—.

[0197] The preferred meaning of E₁₅ is, however, —CO—C(E₁₈)═CHE₁₄, E₁₈and E₁₉ are preferably methyl and especially hydrogen.

[0198] E₂ is —CH₂—CH₂—O—CO—C(G)═CH₂ and G is hydrogen or methyl.

[0199] The instant invention also pertains to a composition stabilizedagainst thermal, oxidative or light-induced degradation which comprises,

[0200] (a) an organic material subject to thermal, oxidative orlight-induced degradation, and

[0201] (b) an effective stabilizing amount of a compound of formula I,II, III or IV.

[0202] Preferably, the organic material is a natural, semi-synthetic orsynthetic polymer, especially a thermoplastic polymer.

[0203] Most preferably, the polymer is a polyolefin or polycarbonate,especially polyethylene or polypropylene; most especially polypropylene;or the polymer is a styrenic, ABS, a nylon, a polyester such aspoly(ethylene terephthalate) or poly(butylene terephthalate), apolyurethane, an acrylate, a rubber modified styrenic, poly(vinylchloride), poly(vinyl butyral), polyacetal (polyoxymethylene),poly(ethylene naphthalene-dicarboxylate), or other blends or copolymerssuch as poly(ethylene/1,4cyclohexylene-dimethylene terephthalate) PETGor an ionomer as described on page 29.

[0204] In another preferred embodiment of the instant invention, theorganic material is a resin selected from the group consisting of athermoset acrylic melamine resin, an acrylic urethane resin, an epoxycarboxy resin, a silane modified acrylic melamine, an acrylic resin withcarbamate pendant groups crosslinked with melamine or an acrylic polyolresin crosslinked with melamine containing carbamate groups.

[0205] Most preferably, the resin is a thermoset acrylic melamine resinor an acrylic urethane resin.

[0206] In yet another preferred embodiment of the instant invention, theorganic material is a recording material.

[0207] The recording materials according to the invention are suitablefor pressure-sensitive copying systems, photocopying systems usingmicrocapsules, heat-sensitive copying systems, photographic materialsand ink jet printing.

[0208] The recording materials according to the invention aredistinguished by an unexpected improvement in quality, especially withregard to the fastness to light.

[0209] The recording materials according to the invention have theconstruction known for the particular use. They consist of a customarycarrier, for example, paper or plastic film, which has been coated withone or more layers. Depending on the type of material, these layerscontain the appropriate necessary components, in the case ofphotographic materials, for example, silver halide emulsions, dyecouplers, dyes and the like. Material particularly suitable for ink jetprinting has a layer particularly absorptive for ink on a customarycarrier. Uncoated paper can also be employed for ink jet printing. Inthis case the paper acts at the same time as the carrier material and asthe ink-absorbent layer. Suitable material for ink jet printing is, forexample, described in U.S. Pat. No. 5,073,448 which is incorporatedherein by reference.

[0210] The recording material can also be transparent as, for example,in the case of projection films.

[0211] The compounds of formula I, II, III or IV can be incorporatedinto the carder material as early as the production of the latter, inthe production of paper, for example, being added to the paper pulp. Asecond method of application is to spray the carder material with anaqueous solution of compounds of formula I, II, III or IV or to add thecompounds to the coating composition.

[0212] Coating compositions intended for transparent recording materialssuitable for projection cannot contain any particles which scatterlight, such as pigments and fillers.

[0213] The dye-binding coating composition can contain a number of otheradditives, for example, antioxidants, light stabilizers (including alsoUV absorbers which do not fall under the scope of the UV absorbers ofthis invention), viscosity improvers, fluorescent brighteners, biocidesand/or antistatic agents.

[0214] The coating composition is usually prepared as follows: thewater-soluble components, for example, the binder, are dissolved inwater and stirred together, the solid components, for example, fillersand other additives already described, are dispersed in this aqueousmedium; and disperison is advantageously carried out by means ofdevices, for example, ultrasonic systems, turbine stirrers,homogenizers, colloid mills, bead mills, sand mills, high-speed stirrersand the like. The compounds of formula I, II, m or IV can be easilyincorporated into the coating composition.

[0215] The recording material according to this invention preferablycontains 1 to 5000 mg/m², in particular 50-1200 mg/m², of a compound offormula I.

[0216] As already mentioned, the recording materials according to theinvention embrace a wide field. The compounds of formula I, II, III orIV can, for example, be employed in pressure-sensitive copying systems.They can be introduced either into the paper in order to protect themicroencapsulated dye precursors there from light, or into the binder ofthe developer layer in order to protect the dyes formed there.

[0217] Photocopying systems using light-sensitive microcapsules whichare developed by means of pressure are described in U.S. Pat, Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463; 4,551,407;4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A 162,664; EP-A164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129. In all thesesystems, the compounds can be put into the dye-receiving layer. Thecompounds can, however, also be put into the donor layer in order toprotect the color formers from light.

[0218] Photographic materials which can be stabilized are photographicdyes and layers containing such dyes or precursors thereof, for example,photographic paper and films. Suitable materials are, for example,described in U.S. Pat. No. 5,364,749 which is incorporated herein byreference. The compounds of formula I, II, III or IV act here as a UVfilter against electrostatic flashes. In color photographic materials,couplers and dyes are also protected against photochemicaldecomposition.

[0219] The instant compounds can be used for all types of colorphotographic materials. For example, they can be employed for colorpaper, color reversal paper, direct-positive color material, colornegative film, color positive film, color reversal film and the like.They are preferably used inter alia for photographic color materialwhich contains a reversal substrate or form positives.

[0220] Color-photographic recording materials usually contain, on asupport, a blue-sensitive and/or a green-sensitive and/or ared-sensitive silver halide emulsion layer and, if desired, a protectionlayer, with the instant compounds being, preferably, either in thegreen-sensitive or the red-sensitive layer or in a layer between thegreen-sensitive and the red-sensitive layer or in a layer on top of thesilver halide emulsion layers.

[0221] The compounds of formula I, II, III or IV can also be employed inrecording materials based on the principles of photopolymerization,photoplasticization or the rupture of microcapsules, or in cases whereheat-sensitive and light-sensitive diazonium salts, leuko dyes having anoxidizing agent or dye lactones having Lewis acids are used.

[0222] Furthermore, the instant compounds can be employed in recordingmaterials for dye diffusion transfer printing, thermal wax transferprinting and non-matrix printing and for use with electrostatic,electrographic, electrophoretic, magnetographic andlaser-electrophotographic printers and pen-plotters. Of the above,recording materials for dye diffusion transfer printing are preferred,for example, as described in EP-A 507,734.

[0223] The instant compounds can also be employed in inks, preferablyfor ink jet printing, for example, as described in U.S. Pat. No.5,098,477 which is incorporated herein by reference.

[0224] The compounds of this invention exhibit superior hydrolyticstability, handling and storage stability as well as good resistance toextractability when present in a stabilized composition.

[0225] The methodology to make the instant compounds is described in theprior art. The intermediates needed to make the instant compounds arelargely items of commerce.

[0226] Preferred compounds are those in which one of X and Y is —O—; andparticularly those in which both X and Y are —O—.

[0227] In general polymers which can be stabilized include

[0228] 1. Polymers of monoolefins and diolefins, for examplepolypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyisoprene or polybutadiene, as well as polymers of cycloolefins, forinstance of cyclopentene or norbornene, polyethylene (which optionallycan be crosslinked), for example high density polyethylene (HDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),branched low density polyethylene (BLDPE).

[0229] Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

[0230] a) radical polymerisation (normally under high pressure and atelevated temperature).

[0231] b) catalytic polymerisation using a catalyst that normallycontains one or more than one metal of groups IVb, Vb, VIb or VIII ofthe Periodic Table. These metals usually have one or more than oneligand, typically oxides, halides, alcoholates, esters, ethers, amines,alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated.These metal complexes may be in the free form or fixed on substrates,typically on activated magnesium chloride, titanium(III) chloride,alumina or silicon oxide. These catalysts may be soluble or insoluble inthe polymerisation medium. The catalysts can be used by themselves inthe polymerisation or further activators may be used, typically metalalkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metalalkyloxanes, said metals being elements of groups Ia, IIa and/or IIa ofthe Periodic Table. The activators may be modified conveniently withfurther ester, ether, amine or silyl ether groups. These catalystsystems are usually termed Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

[0232] 2. Mixtures of the polymers mentioned under 1), for examplemixtures of polypropylene with polyisobutylene, polypropylene withpolyethylene (for example PP/HDPE, PP/LDPE) and mixtures of differenttypes of polyethylene (for example LDPE/HDPE).

[0233] 3. Copolymers of monoolefins and diolefins with each other orwith other vinyl monomers, for example ethylene/propylene copolymers,linear low density polyethylene (LLDPE) and mixtures thereof with lowdensity polyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/-isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

[0234] 4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

[0235] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0236] 6. Copolymers of styrene or α-methylstyrene with dienes oracrylic derivatives, for example styrene/butadiene,styrene/acrylonitrile, styrene/alkyl methacrylate,styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate,styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate;mixtures of high impact strength of styrene copolymers and anotherpolymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

[0237] 7. Graft copolymers of styrene or a-methylstyrene, for examplestyrene on polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

[0238] 8. Halogen-containing polymers such as polychloroprene,chlorinated rubbers, chlorinated or sulfochlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

[0239] 9. Polymers derived from α,β-unsaturated acids and derivativesthereof such as polyacrylates and polymethacrylates; polymethylmethacrylates, polyacrylamides and polyacrylonitriles, impact-modifiedwith butyl acrylate.

[0240] 10. Copolymers of the monomers mentioned under 9) with each otheror with other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

[0241] 11. Polymers derived from unsaturated alcohols and amines or theacyl derivatives or acetals thereof, for example polyvinyl alcohol,polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinylmaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine;as well as their copolymers with olefins mentioned in 1) above.

[0242] 12. Homopolymers and copolymers of cyclic ethers such aspolyalkylene glycols, polyethylene oxide, polypropylene oxide orcopolymers thereof with bisglycidyl ethers.

[0243] 13. Polyacetals such as polyoxymethylene and thosepolyoxymethylenes which contain ethylene oxide as a comonomer;polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

[0244] 14. Polyphenylene oxides and sulfides, and mixtures ofpolyphenylene oxides with styrene polymers or polyamides.

[0245] 15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

[0246] 16. Polyamides and copolyamides derived from diamines anddicarboxylic acids and/or from aminocarboxylic acids or thecorresponding lactams, for example polyamide 4, polyamide 6, polyamide6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromaticpolyamides starting from m-xylene diamine and adipic acid; polyamidesprepared from hexamethylenediamine and isophthalic or/and terephthalicacid and with or without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

[0247] 17. Polyureas, polyimides, polyamide-imides andpolybenzimidazoles.

[0248] 18. Polyesters derived from dicarboxylic acids and diols and/orfrom hydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

[0249] 19. Polycarbonates and polyester carbonates.

[0250] 20. Polysulfones, polyether sulfones and polyether ketones.

[0251] 21. Crosslinked polymers derived from aldehydes on the one handand phenols, ureas and melamines on the other hand, such asphenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

[0252] 22. Drying and non-drying alkyd resins.

[0253] 23. Unsaturated polyester resins derived from copolyesters ofsaturated and unsaturated dicarboxylic acids with polyhydric alcoholsand vinyl compounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

[0254] 24. Crosslinkable acrylic resins derived from substitutedacrylates, for example epoxy acrylates, urethane acrylates or polyesteracrylates.

[0255] 25. Alkyd resins, polyester resins and acrylate resinscrosslinked with melamine resins, urea resins, polyisocyanates or epoxyresins.

[0256] 26. Crosslinked epoxy resins derived from polyepoxides, forexample from bisglycidyl ethers or from cycloaliphatic diepoxides.

[0257] 27. Natural polymers such as cellulose, rubber, gelatin andchemically modified homologous derivatives thereof, for examplecellulose acetates, cellulose propionates and cellulose butyrates, orthe cellulose ethers such as methyl cellulose; as well as rosins andtheir derivatives.

[0258] 28. Blends of the aforementioned polymers (polyblends), forexample PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.

[0259] 29. Naturally occurring and synthetic organic materials which arepure monomeric compounds or mixtures of such compounds, for examplemineral oils, animal and vegetable fats, oil and waxes, or oils, fatsand waxes based on synthetic esters (e.g. phthalates, adipates,phosphates or trimellitates) and also mixtures of synthetic esters withmineral oils in any weight ratios, typically those used as spinningcompositions, as well as aqueous emulsions of such materials.

[0260] 30. Aqueous emulsions of natural or synthetic rubber, e.g.natural latex or latices of carboxylated styrene/butadiene copolymers.

[0261] 31. Polysiloxanes such as the soft, hydrophilic polysiloxanesdescribed, for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

[0262] 32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

[0263] 33. Radiation curable compositions containing ethylenicallyunsaturated monomers or oligomers and a polyunsaturated aliphaticoligomer.

[0264] 34. Epoxymelamine resins such as light-stable epoxy resinscrosslinked by an epoxy functional coetherified high solids melamineresin such as LSE-4103 (Monsanto).

[0265] In general, the compounds of the present invention are employedin from about 0.01 to about 5% by weight of the stabilized composition,although this will vary with the particular substrate and application.An advantageous range is from about 0.05 to about 3%, and especially0.05 to about 1%. However, some high performance films or in UVabsorbing layers of laminates such as those produced by coextrusion maycontain from 5-15% by weight of the instant compounds. Concentrations of5-10% by weight are typical in certain coextrusion applications.

[0266] The stabilizers of the instant invention may readily beincorporated into the organic polymers by conventional techniques, atany convenient stage prior to the manufacture of shaped articlestherefrom. For example, the stabilizer may be mixed with the polymer indry powder form, or a suspension or emulsion of the stabilizer may bemixed with a solution, suspension, or emulsion of the polymer. Theresulting stabilized polymer compositions of the invention mayoptionally also contain from about 0.01 to about 5%, preferably fromabout 0.025 to about 2%, and especially from about 0.1 to about 1% byweight of various conventional additives, such as the materials listedbelow, or mixtures thereof.

[0267] 1. Antioxidants

[0268] 1.1. Alkylated monophenols, for example,

[0269] 2,6-di-tert-butyl-4-methylphenol

[0270] 2-tert-butyl-4,6-dimethylphenol

[0271] 2,6-di-tert-butyl-4-ethylphenol

[0272] 2,6-di-tert-butyl-4-n-butylphenol

[0273] 2,6-di-tert-butyl-4-i-butylphenol

[0274] 2,6di-cyclopentyl-4-methylphenol

[0275] 2-(α-methylcyclohexyl)-4,6-dimethylphenol

[0276] 2,6-di-octadecyl-4-methylphenol

[0277] 2,4,6-tri-cyclohexylphenol

[0278] 2,6-di-tert-butyl-4-methoxymethylphenol

[0279] 1.2. Alkylated hydroquinones, for example,

[0280] 2,6-di-tert-butyl-4-methoxyphenol

[0281] 2,5-di-tert-butyl-hydroquinone

[0282] 2,5di-tert-amyl-hydroquinone

[0283] 2,6-diphenyl-4-octadecyloxyphenol

[0284] 1.3. Hydroxylated thiodiphenyl ethers, for example,

[0285] 2,2 ′-thio-bis-(6-tert-butyl-4-methylphenol)

[0286] 2,2′-thio-bis-(4-octylphenol)

[0287] 4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

[0288] 4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

[0289] 1.4. Alkylidene-bisphenols, for example,

[0290] 2,2′-methylene-bis-(6-tert-butyl-4-metylphenol)

[0291] 2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

[0292] 2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

[0293] 2,2′-methylene-bis-(4-methyl-6cyclohexylphenol)

[0294] 2,2′-methylene-bis-(6-nonyl-4-methylphenol)

[0295] 2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

[0296] 2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

[0297] 2,2′-methylene-bis-(4,6-di-tert-butylphenol)

[0298] 2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

[0299] 2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

[0300] 4,4′-methylene-bis-(2,6-di-tert-butylphenol)

[0301] 4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

[0302] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0303] 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

[0304] 1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

[0305]1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

[0306] ethyleneglycolbis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

[0307] di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

[0308]di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

[0309] 1.5. Benzyl compounds, for example,

[0310]1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

[0311] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

[0312] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctylester

[0313] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiolterephthalate

[0314] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

[0315] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate

[0316] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecylester

[0317] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylester, calcium-salt

[0318] 1.6. Acylaminophenols, for example,

[0319] 4-hydroxy-lauric acid anilide

[0320] 4-hydroxy-stearic acid anilide

[0321]2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

[0322] octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

[0323] 1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid with monohydric or polyhydric alcohols, for example, methanoldiethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

[0324] 1.8. Esters ofβ-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with monohydricor polyhydric alcohols, for example, methanol diethylene glycoloctadecanol triethylene glycol 1,6-hexanediol pentaerythritol neopentylglycol tris-hydroxyethyl isocyanurate thiodiethylene glycoldi-hydroxyethyl oxalic acid diamide triethanolamine triisopropanolamine

[0325] 1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionicacid for example,

[0326]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

[0327]N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

[0328] N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

[0329] 1.10 Diarylamines, for example,

[0330] diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and

[0331] 2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and2,4,4-trimethylpentene.

[0332] 2. UV Absorbers and Light Stabilizers

[0333] 2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the5′-methyl-, 3′,5′-di-tert-butyl-, 5′-tert-butyl-,5′-(1,1,3,3-tetramethylbutyl)-, 5-chloro-3′,5′-di-tert-butyl-,5-chloro-3′-tert-butyl-5′-methyl-, 3′-sec-butyl-5′-tert-butyl-,4′-octoxy, 3′,5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

[0334] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,4,2′,4′-trihydroxy- and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0335] 2.3. Esters of optionally substituted benzoic acids for example,phenyl salicylate, 4-tert-butylphenyl salicylate, octylphenylsalicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

[0336] 2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acidethyl ester or isooctyl ester, α-carbomethoxy-cinnamic acid methylester, α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butylester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

[0337] 2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

[0338] 2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tertbutyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetra-methylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

[0339] 2.7. Oxalic acid diamides, for example,4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

[0340] 2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy4(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4(2-acetoxyethoxy)phenyl]-6-(4-chloro-phenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.

[0341] 3. Metal deactivators, for example, N,N′-diphenyloxalic aciddiamide, N-salicylal-N′-salicyloyl-hydrazine,N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

[0342] 4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecyl-pentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

[0343] 5. Compounds which destroy peroxide, for example, esters ofβ-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

[0344] 6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecyl-hydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

[0345] 7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

[0346] 8. Polyamide stabilizers, for example copper salts in combinationwith iodides and/or phosphorus compounds and salts of divalentmanganese.

[0347] 9. Basic co-stabilizers, for example, melamine,polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, ureaderivatives, hydrazine derivatives, amines, polyamides, polyurethanes,alkali metal salts and alkaline earth metal salts of higher fatty acidsfor example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate and Kpalmitate, antimony pyrocatecholate or zinc pyrocatecholate.

[0348] 10. Nucleating agents, for example, 4-tert-butyl-benzoic acid,adipic acid, diphenylacetic acid.

[0349] 11. Fillers and reinforcing agents, for example, calciumcarbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, bariumsulfate, metal oxides and hydroxides, carbon black, graphite.

[0350] 12. Other additives, for example, plasticizers, lubricants,emulsifiers, pigments, optical brighteners, flameproofing agents,anti-static agents, blowing agents and thiosynergists such as dilaurylthiodipropionate or distearyl thiodipropionate.

[0351] 13. Benzofuranones and indolinones, for example those disclosedin U.S. Pat. Nos. 4,325,863, 4,338,244 or 5,175,312, or3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzo-furan-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)-benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7di-tert-butyl-benzofuran-2-one,3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

[0352] The co-stabilizers, with the exception of the benzofuranoneslisted under 13, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

[0353] Further preferred compositions comprise, in addition tocomponents (a) and (b) further additives, in particular phenolicantioxidants, light stabilizers or processing stabilizers.

[0354] Particularly preferred additives are phenolic antioxidants (item1 of the list), sterically hindered amines (item 2.6 of the list),phosphites and phosphonites (item 4 of the list), UV absorbers (item 2of the list) and peroxide-destroying compounds (item 5 of the list).

[0355] Additional additives (stabilizers) which are also particularlypreferred are benzofuran-2-ones, such as described, for example, in U.S.Pat. Nos. 4,325,863, 4,338,244 or 5,175,312.

[0356] The phenolic antioxidant of particular interest is selected fromthe group consisting of n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6di-tert-butyl-p-cresol, 2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.

[0357] A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-tri-methyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

[0358] The hindered amine compound of particular interest is selectedfrom the group consisting of bis(2,2,6,6-tetramethylpiperidin4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5,1-tert-butyl-4-hydroxybenzyl)butylmalonate,4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6tetramethyl-4-hydroxypiperidine and succinic acid, polycondensationproduct of 4,4′-hexamethylenebis-(amino-2,2,6,6-tetra-methylpiperidine)and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4butanetetracarboxylate,tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate, polycondensation product of2,4-dichloro-6-morpholino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate, mixed(1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethyl-piperidin-4-carboxylate),4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4yl)imino],and2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

[0359] A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N′″-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],or2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylaminol-s-triazine.

[0360] The instant composition can additionally contain another UVabsorber selected from the group consisting of the benzotriazoles,s-triazines, the oxanilides, the hydroxybenzophenones, benzoates and theα-cyanoacrylates.

[0361] Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

[0362] Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected fromthe group consisting of

[0363] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

[0364] 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

[0365]2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

[0366]2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl)-2H-benzotriazole;

[0367] 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

[0368]5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

[0369] 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and

[0370]2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzo-triazole.

[0371] Preferably, the other tris-aryl-s-triazine is selected from thegroup consisting of

[0372]2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

[0373] 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

[0374]2,4-bis(2,4-dimethylphenyl)-6[2-hydroxy-4(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;and

[0375]2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)amino]-s-triazine.

[0376] The alkyd resin lacquers which can be stabilized against theaction of light and moisture in accordance with the instant inventionare the conventional stoving lacquers which are used in particular forcoating automobiles (automobile finishing lacquers), for examplelacquers based on alkyd/melamine resins and alkyd/acrylic/melamineresins (see H. Wagner and H. F. Sarx, “Lackkunstharze” (1977), pages99-123). Other crosslinking agents include glycouril resins, blockedisocyanates or epoxy resins.

[0377] The lacquers stabilized in accordance with the invention aresuitable both for metal finish coatings and solid shade finishes,especially in the case of retouching finishes, as well as various coilcoating applications. The lacquers stabilized in accordance with theinvention are preferably applied in the conventional manner by twomethods, either by the single-coat method or by the two-coat method. Inthe latter method, the pigment-containing base coat is applied first andthen a covering coat of clear lacquer over it.

[0378] It is also to be noted that the compounds of the presentinvention are applicable for use in non-acid catalyzed thermoset resinssuch as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyesterresins, optionally modified with silicon, isocyanates or isocyanurates.The epoxy and epoxy-polyester resins are crosslinked with conventionalcross-linkers such as acids, acid anhydrides, amines and the like.Correspondingly, the epoxide may be utilized as the crosslinking agentfor various acrylic or polyester resin systems that have been modifiedby the presence of reactive groups on the backbone structure.

[0379] When used in two-coat finishes, the compounds of the instantinvention can be incorporated in the clear coat or both in the clearcoat and in the pigmented base coat.

[0380] When water-soluble, water miscible or water dispersible coatingare desired ammonium salts of acid groups present in the resin areformed. Powder coating composition can be prepared by reacting glycidylmethacrylate with selected alcohol components.

[0381] The instant benzotriazoles are made by conventional methods forpreparing such compounds. The usual procedure involves the diazotizationof a substituted o-nitroaniline followed by coupling the resultantdiazonium salt with a substituted phenol and reduction of the azobenzeneintermediate to the corresponding desired benzotriazole. The startingmaterials for these benzotriazoles are largely items of commerce or canbe prepared by normal methods of organic synthesis.

[0382] While the instant benzotriazoles with their enhanced durabilityare particularly suited for automotive coating applications, it iscontemplated that they will also be espeically useful in otherapplications where their enhanced durability is required such as insolar films and the like.

[0383] The following examples are for illustrative purposes only and arenot to be construed to limit the scope of the instant invention in anymanner whatsoever.

EXAMPLE 15-Trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0384] a. Diazotization of 4-amino-3-nitro-benzotrifluoride

[0385] To a 500 ml 3-necked flask, equipped with a mechanical stirrer,are added 41.2 g of 4-amino-3-nitro-benzotrifluoride, 52 ml ofconcentrated hydrochloride acid and 100 ml of distilled water. Thestirred solution is cooled to 5° C. and 17.3 g of sodium nitritedissolved in 50 ml of water are added. The solution is stirred at 0 to5° C. for two hours, then filtered and stored at −1° C.

[0386] b. Monoazo Adduct

[0387] To a 1000 ml flask, fitted with a mechanical stirrer, are added40 g of sodium hydroxide dissolved in 200 ml of methanol and 32.4 g of2-α-cumyl-4tert-octylphenol in 50 ml of xylene. The solution is cooledto 5° C. and the diazo solution of 4-amino-nitro-benzotrifluorideprepared in part a. is added at 0 to 5° C. over a two-hour period. Then100 ml of xylene are added and the organic layer is washed with water,aqueous hydrochloride acid, water, aqueous sodium bicarbonate solutionand finally water. The solvent is removed under reduced pressure and theresidue is purified by chromatography (silica gel, heptane:ethyl acetate95:5) to yield 42.1 g of the adduct product as a dark red paste.

[0388] c. Reduction of the Monoazo Adduct

[0389] A 1000 ml flask is charged with 20 g of sodium hydroxide, 40 mlof water, 42.1 g of the monoazo adduct prepared in part b. and 400 ml ofethanol. The mixture is warmed to 80° C. and 27 g of formamidinesulfinic acid is added in portions with stirring. After 1.5 hours, thesolution is cooled to room temperature and 100 ml of water are added.The pH is adjusted to pH 7 with concentrated hydrochloric acid. Theethanol is removed under vacuum and the water layer is extracted withmethylene chloride. The solvent is then evaporated in vacuo and theresidue is purified by chromatography (silica gel, heptane:tolunen 9:1)and crystallized from ethanol. The tide compound is obtained in a yieldof 5.6 g as a pale yellow solid melting at 119-121° C.

EXAMPLE 25-Fluoro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0390] The title compound is prepared according to the general procedureof Example 1 using 31.2 g of 4-fluoro-2-nitroaniline. In part c of theprocedure, an additional 9 g of form amidine sulfinic acid is requiredto complete the reduction. Purification of the crude product on silicagel (heptane:toluene, 1:1) yields 4.5 g of the title compound as aoff-white solid. Further purification by recrystallization fromacetonitrile:toluene provides 1.1 g of the title compound melting at93-96° C.

EXAMPLE 35-Chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0391] The general procedure of Example 1 parts a and b is followed toprepare the monoazo intermediate of making the title compound from 339.3g of 4chloro-2-nitro-aniline. The crude product is purified byrecrystallization from methanol to yield 70.9 g of deep red monoazoadduct.

Reduction of the Monoazo Adduct

[0392] A mixture of 11.8 g of sodium hydroxide and 138 g of 2-butanol isheated to 95° C. A solution of 60.1 g of the above monoazo adduct and1.3 g of 2,3-dichloro-1,4naphthoquinone in 90 g of 2-butanol is addedover a 90 minute period with stirring. The reaction mixture is heated toremove the 2-butanone byproduct with additional 2-butanol added toreplace the distillate. The reaction mixture is cooled to 85° C., washedwith 2.5 N sulfuric acid and brine and then concentrated. The residue isrecrystallized from methanol:xylene to yield 45.6 g of the titlecompound as a light yellow solid melting at 104-105° C.

EXAMPLE 45-Phenylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0393] To a stirred mixture of 75 g of5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazoleand 105 g of N-methylpyrrolidone heated at 90° C. is added first 44.3 gof 45% aqueous potassium hydroxide solution over a 15-minute period then20.4 g of thiophenol over another 15 minutes. The reaction mixture isthen heated at 170-175° C. for four hours with water being removed bydistillation. After cooling to 100° C., xylene and water are added andthe resultant mixture is made acidic with 15% aqueous hydrogen chloridesolution. The organic layer is separated and washed with water and thenconcentrated. The crude product residue is recrystallized from methanolto yield 82 g of the title compound as a pale yellow solid melting at124-125° C.

EXAMPLE 55-Benzenesulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0394] A 1000 mL flask is charged with 75.2 g of5-phenylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 4, 102 g of xylene, 0.9 g of sodium tungstatedihydrate and 18.4 g of formic acid. The mixture is heated to 50° C. Tothis stirred mixture is slowly added 36.3 g of 50% hydrogen peroxide sothat the temperature does not exceed 85° C. Additional xylene and waterare then added. The organic layer is separated, washed with aqueoussodium sulfite, then twice with water and concentrated. The crudeproduct residue is recrystallized from methanol to yield 75.2 g of thetide compound as a light yellow solid melting at 170-171° C.

EXAMPLE 65-Nonylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0395] Using the procedure of Example 4 with 30 g of5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole and17.6 g of nonyl mercaptan, the title compound is prepared.

EXAMPLE 7

[0396]5-Nonylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0397]5-Nonylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 6, is oxidized to the sulfone without purificationof the thio intermediate using 8.7 g of formic acid, 0.7 g of sodiumtungstate dihydrate and 17.6 g of 50% hydrogen peroxide to yield thetitle compound as a yellow resin exhibiting a molecular ion of m/e 631.This process is described in detail in copending application Serial No.______.

EXAMPLE 8

[0398]5-Chloro-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0399] The general procedure of Example 1 parts a and b are used toprepare the monoazo intermediate for the title compound from4-chloro-2-nitroaniline and 2-phenyl-4-tert-octylphenol. The crudeproduct is purified by recystallization from methanol to yield a deepred monoazo adduct.

[0400] The title compound is prepared according to the reductionprocedure of Example 3 from 65 g of the monoazo adduct prepared above,19.9 g of sodium hydroxide and 2.4 g of 2,3-dichloro-1,4-naphthoquinone.The crude product is purified by chromatography on silica gel(hexane:ethyl acetate, 5:1) yielding a fraction which is predominantlythe title compound exhibiting a molecular ion of m/e 433.

EXAMPLE 95-Phenylthio-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0401] The title compound is prepared according to the procedure ofExample 4 from 20 g of the compound of Example 8, 20.4 g of 45% aqueouspotassium hydroxide, 10.3 g of thiophenol and 100 g ofN-methylpyrrolidone. The title compound is an oil purified bychromatography on silica gel using toluene as eluent.

EXAMPLE 105-Benzenesulfonyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole

[0402] The title compound is prepared according to the procedure ofExample 5 from 20 g of the thio compound of Example 9, 6.4 g of formicacid, 15.0 g of 50% hydrogen peroxide and 0.6 g of sodium tungstatedihydrate. Recrystallization of 2.5 g of crude material fromxylene/methanol yields 2.0 g of the purified title compound as a lightyellow powder melting at 204-206° C.

EXAMPLE 11 Mixture of5-Chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkyl beingindependently C₄, C₈, C₁₂ and C₁₆)

[0403] A mixture of 65.4 g of5-chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzo-triazole, 45 mL ofdodecene and 13 mL of methane sulfonic acid is heated to 170° C. undernitrogen. An additional 135 mL of dodecene is added over a 4.5 hourperiod. The reaction mixture is allowed to cool to 100° C. and thenquenched with 400 g of crushed ice and extracted thrice with ethylacetate. The organic layers are combined, washed with water, aqueoussodium bicarbonate, water again and brine, dried over anhydrousmagnesium sulfate and finally concentrated. The polymeric residue isremoved by bulb to bulb distillation under vacuum at 0.2 mm and up to210° C. Unreacted starting material is then removed by distillation (at0.01 mm,160° C.) to give 45 g of the title mixture as a yellow oil.

EXAMPLE 12 Mixture of5-Phenylthio-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkylbeing independently C₄, C₈, C₁₂ and C₁₆)

[0404] The title mixture is prepared according to the procedure ofExample 4 using 40 g the mixture of Example 11, 11.2 g of potassiumhydroxide and 12.3 mL of thiophenol.

EXAMPLE 13 Mixture of5-Benzenesulfonyl-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole(Alkyl being Independently C₄, C₈s, C₁₂ and C₁₆)

[0405] A mixture of the crude product of Example 12, 350 mL ofisopropanol, 14.7 mL of formic acid and 1.8 mL of concentrated sulfuricacid are heated to reflux and 30 mL of 50% hydrogen peroxide is addeddropwise over a two-hour period. After an additional three hours atreflux, the reaction mixture is cooled and 10% aqueous sodium sulfiteand aqueous sodium bicarbonate are added. The isopropanol is evaporatedand the residue is extracted with methylene chloride. The organic layeris washed with water and then dried over anhydrous magnesium sulfate.The solution is concentrated to leave 45 g of crude product as a viscousprange oil. Some 30 g of this crude product is purified bychromatography on silica gel (heptane:ethyl acetate, 4:1) to yield 28.9g of the title mixture as a yellow oil.

EXAMPLE 145-Diphenylphosphinyl-2-(2-hydroxy-3,5-tert-butylphenyl)-2H-benzotriazole

[0406] To a flame-dried 500 mL three-necked round-bottomed flaskequipped with a condenser, magnetic stirrer and thermometer are charged100 mL of dimethyl sulfoxide, 7.41 g (0.066 mol) of potassiumtert-butoxide and 11.17 g (0.060 mol) of diphenyl-phosphine via asyringe. A slurry of 10.56 g (0.030 mol) of5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole in 50 mLof dimethyl sulfoxide is added all at once to the red mixture. Theresultant brown solution is stirred at 135° C. for 3.5 hours and thencooled to room temperature. The mixture is quenched with a portion ofsaturated ammonium chloride solution and ethyl acetate is then added.The organic layer is separated and washed thrice with water, once withbrine and then dried over anhydrous magnesium sulfate. To the solutionis added 50% hydrogen peroxide resulting in an exotherm. The mixture isallowed to sit for 30 minutes, then washed once with 10% sodiummetabisulfite solution thrice with saturated sodium bicarbonate solutiononce with brine and finally dried over anhydrous magnesium sulfate. Themixture is filtered with a plug of silica gel and the solvent is removedunder reduced pressure to yield 8.0 g of a crude yellow solid. The crudeproduct is treated with medium pressure chromatography usingheptane:ethyl acetate, 1:1 to afford 4.2 g (27% yield) of the tidecompound as a yellow solid melting at 98-100° C.

EXAMPLE 155-Diphenylphosphinyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0407] Following the procedure of Example 14, the title compound isprepared when5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole isused as the starting benzotriazole intermediate.

EXAMPLES 16-26

[0408] Following the general procedure of Example 1, the followingadditional 2H-benzotriazoles of formula I are prepared. Example G₂ E₁ E₂16 CF₃ phenyl tert-octyl 17 CF₃ α-cumyl tert-butyl 18 CN α-cumyltert-octyl 19 CN α-cumyl nonyl 20 CN α-cumyl tert-butyl 21 COOCH₃α-cumyl dodecyl 22 F phenyl tert-octyl 23 CF₃ α-cumyl nonyl 24 CF₃α-cumyl dodecyl 25 CON(Bu)₂ α-cumyl tert-octyl 26 COOCH₃ phenyltert-octyl

EXAMPLE 275-Octylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0409] Using the procedure of Example 6 with5-chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole andoctyl mercaptan, the title compound is prepared.

EXAMPLE 285-Octylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0410]5-Octylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 27, is oxidized to the sulfone without purificationof the thio intermediate using the general method of Example 7. A yellowresinous liquid is obtained whose structure is consistent as measured by¹HNMR.

EXAMPLE 295-Carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazolea. Esterification of 4-amino-3-nitrobenzoic Acid

[0411] To a 2 L 3-necked flask fitted with a mechanical stirrer areadded 700 mL of methanol, 20 g of xylene, 14 g concentrated sulfuricacid and 100 g of 4-amino-3-nitro-benzoic acid. The solution is heatedto reflux for 33 hours. The mixture is cooled to 35° C. and neutralizedto pH 7.8. Water (1 L) is added, the solid collected and washed with 500ml to give after drying overnight 100.9 g of methyl4-amino-3-nitrobenzoate.

b. Diazotization of Methyl 4-amino-3-nitrobenzoate

[0412] To a 1 L 3-necked flask fitted with a mechanical stirrer is added177 g of 96% sulfuric acid and then slowly over 90 minutes 11 g ofsodium nitrite. The mixture is warmed to 30° C. to initiate thereaction. The temperature is kept below 70° C. The mixture is thencooled to 15° C. and 30 g of methyl 4-amino-3-nitrobenzoate is addedover two hours keeping the temperature between 15-20° C. The mixture iscooled to 0c and 200 g of ice is added to make the solution suitable forthe coupling reaction to form a monoazo compound.

c. Monoazo Adduct

[0413] To a 2 L 3-necked flask fitted with a mechanical stirrer andaddition funnel are added 52 g of 2-α-cumyl-4-tert-octylphenol, 20 g ofwater, 315 g of methanol, 7 g of xylene and 150 g of sodium hydroxide.The mixture is cooled to −5° C. and the diazonium salt solution preparedis step b. is added over a two hour period with cooling to keep thetemperature below 3° C. After the diazonium salt solution is added, thepH is adjusted to 6.5-7.0. The mixture is poured into 500 mL of xyleneand washed thrice with 500 mL of water at 60° C. The xylene is removedby distillation to give 186 g of the monoazo adduct containing residualxylene.

d. Reduction of the Monoazo Adduct

[0414] To a 500 mL flask fitted with a mechanical stirrer is added the186 g of monoadduct prepared in step c., 125 g of 2-butanol and 1.7 g of2,3-dichloro-1,4naphtho-quinone. The mixture is heated to 90° C. and theresulting solution is then charged to the addition funnel on a separateflask. In said second flask are added 175 g of 2-butanol and 18.6 g ofsodium hydroxide, The flask is heated to 95° C. and the monoazo solutionis added over two hours while distilling off methyl ethyl ketone and2-butanol. 2-Butanol (100 g) is added and an azeotrope is distilled off.The mixture is then cooled and 300 g of xylene and 200 mL of water areadded. The pH is adjusted to 7-7.5 with 20% sulfuric acid. At 60° C.,the aqueous phase is separated and the organic phase washed twice with200 mL of water. The xylene is removed by distillation and the residueformed is crystallized from methanol to give 8.8 g of the title compoundmelting at 141-143° C.

EXAMPLE 305-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl]-2H-benzotriazolea. Saponification of5-Carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0415] To a 250 mL 3-necked flask equipped with a mechanical stirrer,thermometer, condenser and nitrogen inlet is added 1.8 g of potassiumhydroxide and 40 mL of methanol. The mixture is warmed to 40° C. todissolve the potassium hydroxide. To this solution is added 2.7 g of5-carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,prepared in Example 36, in 40 mL of methanol. The reaction mixture isrefluxed for six hours. The mixture is then cooled and acidified withhydrochloric acid. Ether and ethyl acetate are added, and the organiclayer is separated and dried over anhydrous sodium sulfate. After vacuumstripping of the solvent, 2.5 g of5-carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole isisolated.

b.5-Chlorocarbonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0416] The 2.5 g of5-carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzo-triazole,prepared in step a., are placed in a 250 mL flask equipped with astirrer, thermometer, reflux condenser, Dean-Stark trap and nitrogeninlet Toluene (100 mL) is added and the mixture is reflux to remove anytraces of water. The mixture is then cooled and 0.76 g of oxalylchloride in 15 mL of toluene is added. The reaction mixture is heatedslowly to 60° C. and held at 60-65° C. for eight hours till all thehydrogen chloride is expelled to give the acid chloride title compound.

c.5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-α-cumyl-5-tert-octyl)phenyl]-2H-benzotriazole

[0417] To a 500 mL flask equipped with a mechanical stirrer, dryingtube, thermometer and dropping funnel are added 0.8 g ofdi-n-butylamine, 6 mL of pyridine and 25 mL of toluene. The mixture iscooled to 0° C. and the acid chloride solution prepared in step b. isplaced in the dropping funnel and added to the reaction mixture over a30-minute period at −5° C. to −10° C. The reaction mixture is stirred atthat temperature for 1.5 hours and then held at ambient temperatureovernight. The mixture was filtered and then vacuum stripped to give 3.0g of crude solids. The solid product is chromatographed to provide 1.2 gof the title compound as a tan solid melting at 131-133° C. Thestructure is confirmed by nmr and mass spectrometry m/z 596.

EXAMPLE 315-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole

[0418] The title compound is prepared according to general procedure ofExample 1 the diazo compound of 4-amino-3-nitrobenzotrifluoride and4-tert-octylphenol, and which is purified by chromatography on silicagel. Recrystallization of the product from either heptane or methanolyields the title compound as a near white solid melting at 80-81° C.

EXAMPLE 325-n-Butylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

[0419] 5-Chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole(21.2 g, 0.06 mol), n-butyl mercaptan (7.2 g, 0.08 mol), potassiumhydroxide (6.7.1 g, 0.12 mol) and N-methylpyrrolidone (50 g, 0.5 mol)are charged to a reactor and heated to 150° C. The reaction mass is heldat 150° C. for 4.5 hours at which time it then cooled to ambienttemperature. A mixture of 15 g of concentrated hydrochloric acid aand 70g of ice are then added to the reactor. The solids are filtered off andwashed with water. Thirty gram of crude, wet, yellow crystals areobtained as the tide compound. This product can be used “as is” inprocedure of Example 33.

EXAMPLE 335-n-Butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

[0420] The product as prepared in Example 32 (39.5 g, 0.1 mol), formicacid (10 g, 0.2 mol), sodium tungstate (0.33 g, 0.001 mol) and xylenes(100 mL) are charged to a reactor and heated to 50° C. Hydrogen peroxide(27.2 g, 0.4 mol) is charged dropwise over a one-hour period. Thetemperature is raised to 75° C. and held there for four hours. Thereaction is judged complete using thin layer chromatography. The aqueouslayer is split off and the organic phase is washed successively with 100mL of sodium sulfite solution, twice with sodium bicarbonate solution,with saturated sodium chloride solution and then water. Xylene isstripped off and the crude product is crystallized from ethanol andheptane. Thirty grams of the title compound are obtained as yellowneedles melting at 156° C. The structure is verified by ¹Hnmr analysis.

EXAMPLE 342-[2-Hydroxy-3-(di-n-butylaminomethyl)-5-tert-ctylphenyl]-2H-benzotriazole

[0421] 2-[2-Hydroxy-5-tert-octylphenyl]-2H-benzotriazole (30 g, 0.092mol), paraformaldehyde (3 g, 0.0955 mol) and di-n-butylamine (24.9 g,0.191 mol) are charged to a pressure reaction at ambient temperature.The reactor is sealed and the temperature raised to 160° C. The reactionmass is held at 160° C. for four hours and then discharged. The reactoris rinsed with toluene. The toluene, amine and water are stripped byrotary evaporation. The crude product is prepared in a 96% yield (40 g).This product is chromatographed on silica gel using a heptane/ethylacetate gradient as eluent to remove a trace of unreacted startingbenzotriazole intermediate. The tide compound is a yellow oil whosestructure is confirmed by ¹Hnmr.

EXAMPLE 35Methylene-[2-(4-tert-octyl-6-²H-benzotriazol-2-yl)phenol]{2′-[4-tert-octyl-6-(5-trifluoromethyl)-2H-benzotriazol-2-yl}phenol}

[0422] Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole(10 g, 0.025 mol, as prepared in Example 31), sodium methoxide (1.49 g,0.026 mol) and xylenes (20 g, 0.187 mol) are added to a reaction flaskwhich is then heated to 160° C. The compound prepared in Example 34(11.75 g, 0.0253 mol) dissolved in 11.8 g of xylenes is dripped into thereaction mass over a one-hour period. At the end of the addition, thereaction mass is heated to 205° C. while distilling off xylene, methanoland di-n-butylamine. After one hour at 205° C., the reaction mass issubjected to a 26″ Hg vacuum for three hours. After the vacuum isreleased, the reaction mass is cooled to 100° C. and 100 g of heptane ischarged. The solution is then washed with 50 g of 10% aqueoushydrochloric acid followed by 50 g of water. The heptane is dried andthe product is crystallized and isolated by filtration. After washingthe filter cake with heptane, the product is dried to constant weight invacuo. The title compound is obtained as a solid (16 g, 87% yield)melting at 163-166° C.

[0423] Analysis:

[0424] Mass spectrometry: 727 (M+H);

[0425]¹Hnmr (CDCl₃): δ0.71 (s, 9H), 0.72 (s, 9H), 1.40 (s, 6H), 1.41 (s,6H) 1.74 (s, 2H), 1.75 (s, 2H), 4.31 (s, 2H), 7.38 (d, 1H), 7.42 (d,1H), 7.48 (complex, 2H), 7.68 (dd, 1H), 7.95 (complex, 2H), 8.08 (d,1H), 8.29-8.33 (3d, 3H), 11.54 (s, 1H)

EXAMPLE 365-n-Butylthio-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0426]5-Chloro-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole(38.1 g, 0.08 mol), n-butyl mercaptan (9 g, 0.10 mol), potassiumhydroxide (10.1 g, 0.18 mol) and N-methylpyrrolidone (99 g, 1.0 mol) arecharged to a reactor and heated to 170° C. The reaction mass is held at170° C. with vigorous stirring for five hours. The reaction is judged ascomplete using thin layer chromatogrphy. The temperature is reduced to5° C. and 100 mL of aqueous 2N hydrochloric acid are then added to thereactor. The liquid is decanted and the solids are dissolved in ethylacetate. The organic layer is washed with aqueous 2N hydrochloric acidfollowed by water. The ethyl acetate is stripped off and the product iscrystallized from ethanol and toluene. The tide compound is obtained asa yellow crystalline product in 83% yield. The structure is verified by¹Hnmr.

EXAMPLE 375-n-Butylsulfonyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

[0427] The product prepared in Example 36 (34.2 g, 0.065 mol), formicacid (6.8 g, 0.13 mol), sodium tungstate (0.21 g, 0.00065 mol) andxylenes (100 mL) are charged to a reactor and heated to 50° C. Hydrogenperoxide (17.7 g, 0.26 mol) is charged dropwise over a one-hour period.After the addition is complete, the reaction mass is held at 50° C. for3.5 hours. The reaction is judged complete using thin layerchromatography. The reaction mass is washed with 230 g of 14% sodiumsulfite solution after the addition of 200 mL of xylene. The organicphase is washed with 200 mL of saturated sodium bicarbonate solution,with 100 mL of saturated sodium chloride solution and then with 200 mLof water. Xylene is stripped off to give a yellow oil whichcrystallized. The crude product is recrystallized from toluene/methanolto give a 55% yield of the tide compound as a solid melting at 118° C.The structure is verified by ¹Hnmr and mass spectrometry analysis.

EXAMPLE 38 Methyl3-(Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

[0428] The general procedure of Example 1, parts a and b, is followed toprepare the unisolated, solid, monoazo intermediate of the titlecompound from 62.5 g of 4-amino-3-nitrobenzotrifluoride(=4-trifluoromethyl-o-nitroaniline).

[0429] The monoazo intermediate (84 g, 0.19 mol), xylenes (116 g, 1.08mol), diethylamine (100 g, 1.4 mol) and 5% palladium on charcoal (0.5 g,50% assay) are charged to a reactor. Hydrazine (27.4 g, 0.56 mol) isdripped in over a two-hour period at a temperature range of 15-45° C.After the addition is complete, the temperature is raised to 80° C. andheld there for three hours. The reaction is judged complete by thinlayer chromatography. The catalyst is removed by filtration and thesolvent removed in vacuo to yield 36 grams of the product. Afterrecrystallization from methanol, the title compound is obtained as lightyellow needles melting at 105-107° C.

[0430] Analysis:

[0431] Mass spectrometry: 422 (M+H);

[0432]¹Hnmr (CDCl₃): δ1.51 (s, 9H), 2.71 (t, 2H), 3.02 (t, 2H), 3.71 (s,3H), 7.26 (d, 1H), 7.69 (dd, 1H), 8.07 (d, 1H), 8.17 (d, 1H), 11.55 (s,1H)

EXAMPLE 393-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicAcid

[0433] The ester prepared in Example 38 (36 g, 0.088 mol), sodiumhydroxide (16.4 g, 0.41 mol), N-methylpyrrolidone (12 g, 0.12 mol) andwater (400 g) are charged to a reactor and heated to 100° C. Thesolution is refluxed for three hours after which the reaction mass ispoured into 500 g of 10% aqueous hydrochloric acid. The solids areremoved by filtration, washed with water and dried to a constant weightto give 31.6 g of product. This material is recrystallized fromtoluene/acetone to give the title compound as a light yellow solidmelting at 166° C.

[0434] Analysis:

[0435] Mass spectrometry: 406 (M−H);

[0436]¹Hnmr (CDCl₃): δ1.50 (s, 9H), 2.78 (t, 2H), 3.04 (t, 2H), 7.26 (d,1H), 7.65 (dd, 1H), 8.07 (d, 1H), 8.18 (d, 1H), 8.31 (d, 1H), 11.58 (s,1H)

EXAMPLE 40 Isooctyl3-(Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

[0437] The acid prepared in Example 39 (8 g, 0.02 mol), EXXAL® 8(isooctanol isomers, Exxon, 5 g, 0.038 mol), p-toluenesulfonic acidhydrate (0.5 g, 0.0026 mol) and xylenes (100 mL) are charged to areactor and refluxed for six hours. TLC shows when the reaction iscomplete. The solvent is removed and the resulting oil ischromatographed on silical gel. The title compound is obtained in 99.5%yield as a light yellow oil.

[0438] Analysis:

[0439] Mass spectrometry: 520 (M+H);

[0440]¹Hnmr (CDCl₃): δ0.73-1.79 (broad complex, 15H), 1.51 (s, 9H), 2.71(t, 2H), 3.02 (t, 2H), 4.10 (complex, 2H), 7.27 (d, 1H), 7.69 (dd, 1H),8.08 (d, 1H), 8.18 (d, 1H), 8.30 (s, 1H), 11.55 (s, 1H)

EXAMPLE 415-Trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole

[0441] Following the general procedure of Example 1, 62.5 g of4-amino-3-nitro-benzotrifluoride is used to make 42.5 g of the titlecompound which is obtained as yellow crystals melting at 100.5-101.5° C.

[0442] Analysis:

[0443]¹Hnmr (CDCl₃): δ0.79 (s, 18H), 1.45 (s, 9H), 1.54 (s, 3H), 1.56(s, 3H), 1.82 (s, 2H), 2.12 (s, 2H), 7.44 (d, 1H), 7.66 (dd, 1H), 8.10(d, 1H), 8.30 (s, 1H), 8.32 (s, 1H), 11.55 (s, 1H)

EXAMPLE 425-Trifluoromethyl-2-(2-hydroxy-3-allyl-5-tert-octyl-phenyl)-2H-benzotriazole

[0444] The compound prepared in Example 31 (13.01 g, 0.033 mol),potassium hydroxide (2.37 g, 0.036 mol) and ethanol (60 mL) are chargedto a reactor and stirred at ambient temperature for two hours. Allylbromide (4.84 g, 0.039 mol) and potassium iodide (0.34 g, 0.002 mol) areadded to the reaction mixture which is heated to 85° C. After holding at85° C. for 4.5 hours, the solvent is removed and replaced with 100 mL ofheptane. The mixture is washed thrice with 40 mL of water. The solventis then removed to yield 14.2 g of the corresponding O-allyl ether as anoff-white solid.

[0445] Analysis:

[0446]¹Hnmr (CDCl₃): δ0.78 (s, 9H), 1.41 (s, 6H), 1.77 (s, 2H),4.60-4.65 (d, 2H), 5.16-5.34 (m, 2H), 5.86-6.00 (m, 1H), 7.06-7.11 (d,1H), 7.49-7.54 (dd, 1H), 7.61-7.67 (m, 2H), 8.08-8.12 (d, 1H), 8.35 (s,1H)

[0447] The O-allyl compound (14.2 g) as prepared above is charged to areactor and heated to 190-195° C. and held at that temperature for fivehours. Flash column chromatography with silica gel and ethylacetate/heptane solvent as eluent to give the title compound in 12.2 gyield as a yellow oil.

[0448] Analysis:

[0449] Mass spectrometry: 432 (M+H);

[0450]¹Hnmr (CDCl₃): δ0.78 (s, 9H), 1.46 (s, 6H), 1.81 (s, 2H),3.53-3.64 (d, 2H), 5.06-5.20 (m, 2H), 6.02-6.18 (m, 1H), 7.29-7.34 (d,1H), 7.66-7.72 (dd, 1H), 8.05-8.12 (d, 1H), 8.29-8.35 (m, 2H), 11.17 (s,1H)

EXAMPLE 432,2′-Methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol]

[0451] The compound prepared in Example 31 (7.0 g, 0.018 mol),paraformaldehyde (0.29 g, 0.0093 mol) and di-n-butylamine (2.43 g,0.0186 mol) are charged to a reaction and which is then sealed. Thetemperature is increased to 160° C. and held there for four hours. Thereaction mass is cooled to 110° C. at which time sodium methoxide (0.16g, 0.0028 mol) is added. The reaction mixture is then heated to 205° C.and held there for three hours. The reaction mass is then cooled to 110°C. and 100 mL of xylenes are added. The reaction mass is neutralizedwith 10% aqueous hydrochloric acid and the organic phase is twice washedwith water. Xylene is then distilled off and replaced with heptane.After cooling the heptane solution, yellow crystals separate out and areisolated by filtration. After drying to constant weight, the titlecompound (5 g) is obtained as a solid melting at 178° C.

[0452] Analysis:

[0453]¹Hnmr (CDCl₃): δ0.72 (s, 18H), 1.41 (s, 12H), 1.75 (s, 4H), 4.31(s, 2H), 7.42 (d, 2H), 7.68 (dd, 2H), 8.08 (d, 2H), 8.31 (d, 4H), 11.25(s, 2H)

EXAMPLE 44 2-(2-Hydroxy-5-trifluoromethylphenyl)-2H-benzotriazole

[0454] The title compound is prepared following the general procedure ofExample 1 starting with o-nitroaniline and 4-trifluoromethylphenol.Rigorous purification of the crude product on silica gel (heptane/ethylacetate 4:1) followed by recrystallization from heptane yields the titlecompound as a yellow solid melting at 119-120° C. The structure isconfirmed by UV spectroscopy, mass spectrometry and ₁Hnmr.

[0455] Analysis:

[0456] Mass spectrometry: m/z 279;

[0457]¹Hnmr (300 mHz, CDCl₃): δ7.31 (d, 1H), 7.54 (m, 2H), 7.61 (dd,1H), 7.97 (m, 2H), 8.74 (d, 1H), 11.75 (s, 1H)

[0458] UV Absorption (ethyl acetate) λ_(max) 328, ε20,500

EXAMPLE 455-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole

[0459] The title compound is prepared by reacting the ester compound ofExample 38 with lithium aluminum hydride according to the procedure ofExample 19 of U.S. Pat. No. 5,280,124. The title compound is obtained in80% yield as a solid melting at 90-91° C.

EXAMPLE 465-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole

[0460] The title compound is prepared by the reaction of the compound ofExample 45 with Methacryloyl chloride in the presence of triethylaminein toluene.

EXAMPLE 47-53

[0461] Following the general procedure of Example 45, the followingcompounds of formula III are prepared where n is 1, m is 2 and E₅ ishydroxy. Example G₁ G₂ E₁ E₃ 47 Cl F tert-butyl — 48 H CF₃ phenyl — 49 HCF₃ allyl — 50 H CN α-cumyl — 51 H E₃SO α-cumyl butyl 52 H E₃SO₂ phenylphenyl 53 E₃SO₂ tert-octyl ethyl

EXAMPLE 545-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole

[0462] When using the general procedure of Example 1 the2-α-cumyl-4-tert-octylphenol is replaced by2-tert-butyl-(2-hydroxyethyl)phenol, the title compound is prepared.

EXAMPLE 555-Trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole

[0463] When using the general procedure of Example 1, the2-α-cumyl-4-tert-octylphenol is replaced by 4-(2-hydroxyethyl)phenol,the tide compound is prepared.

EXAMPLE 565-Trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole

[0464] When using the general procedure of Example 1, the2-α-cumyl-4-tert-octylphenol is replaced by 2,4-di-α-cumyl-phenol, thetitle compound is prepared.

EXAMPLE 575-Trifluoromethyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole

[0465] Using the general procedure of Example 1, 47.1 g of2,4-di-tert-butylphenol is used to prepare 14.1 g of the tide compoundas yellow needles melting at 131-133° C.

EXAMPLE 585-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-aminopropyl)phenyl]-2H-benzotriazole

[0466] The tide compound is prepared by reacting the amide of the acidcompound of Example 39 with lithium aluminum hydride dissolved indiethyl ether according to the general procedure of Example 19 of U.S.Pat. No. 5,280,124.

EXAMPLE 595-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-methacryloylaminopropyl)phenyl]-2H-benzotriazole

[0467] The tide compound is prepared by the reaction of the compound ofExample 58 with methacryloyl chloride in the presence of triethylaminein toluene.

EXAMPLE 60 Isomeric Mixture of3-[3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-2-hydroxypropylMethacrylate and2-[3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-3-hydroxypropylMethacrylate

[0468] Following the general procedure of Example 25 of U.S. Pat. No.5,280,124, the title compounds are prepared from the acid compound ofinstant Example 39 and glycidyl methacrylate in the presence oftetrabromoammonium bromide dissolved in toluene.

EXAMPLE 61-73

[0469] Following the general procedure of Example 45, the followingcompounds of formula III are prepared where n is 1, m is 2 and E₅ is amixture of —OCH₂CHOHCH₂OCOC(CH₃)═CH₂ and —OCH(CH₂OH)CH₂OCOC(CH₃)═CH₂.Example G₁ G₂ E₁ E₃ G₃ 61 Cl F α-cumyl — — 62 H CF₃ phenyl — — 63 H CF₃hydrogen — — 64 H CF₃ cyclohexyl — — 65 H CF₃ tert-octyl — — 66 H CNα-cumyl — — 67 H F phenyl — — 68 Cl CN α-cumyl — — 69 H G₃CO— α-cumyl —methyl 70 H G₃CO— phenyl — phenyl 71 H E₃SO α-cumyl hexyl — 72 H E₃SO₂phenyl HOCH₂CH₂— — 73 H E₃SO₂ phenyl phenyl —

EXAMPLE 74 UV Absorption Data

[0470] The following table demonstrates the enhanced absorption of thecompounds of the instant invention for wavelengths above 350 nm. Whilethe λ max of the instant compounds is not always significantly shiftedrelative to the unsubstituted benzotriazoles, the absorbance is muchgreater as seen by the absorbance at A max. In the following examplesthe absorbance at 375 nm is reported for 20 mg/l concentrations. This isnot the molar extinction values. Compound* λ max nm ε @ λ max Absorbance@ 375 nm Q 345 16,500 0.28 U 362 17,300 0.50 CC 359 14,100 0.42 S 34815,000 0.35 BB 348 14,000 0.33 DD 358 15,700 0.42 EE 328 20,700 0.03

[0471] It is noted that compound EE, prepared in Example 44, is closelyrelated to the compounds disclosed in Japanese Sho 47-15210 and has poorred region absorbance. This is an unwanted property for the UV absorberswhere absorbance in the upper regions (above 350 nm) of the UV spectraare of vital importance.

EXAMPLE 75 Yellowness Color Data

[0472] The following examples show the difference in color between someof the instant compounds as measured by a Macbeth Color-Eye instrumentat a concentration of 30 mg/100 mL in butyl acetate. This shows therelative color of the benzotriazoles having various substituents in theS-position of the benzo ring and in the 3- and 5-positions of the phenylring. In the table, the compounds are listed by increasing b value. Theinstrument measures yellowness as b and DE is the correspondingYellowness Index value. Compound* b DE Q −0.02   0.07 BB 0.20 0.27 FF0.54 0.72 S 1.05 1.28 DD 1.85 2.25 CC 2.84 3.35 U 3.75 4.42

[0473] The compounds not having an α-cumyl moiety in the 3-position ofthe phenyl ring have better color than the compounds having such a groupat that position.

EXAMPLE 76 Yellowness Color Data

[0474] The following example shows the lower color in a polymer resincomposition containing benzotriazole substituted with a trifluoromethylgroup on the benzo ring compared to a similar benzotriazole substitutedby a sulfonyl moiety.

[0475] Test additives are dry blended with polycarbonate pellets(MAKROLON® 2608-1000, Bayer) using a Turbula mixer. The dry blends areextruded and pelletized using a single screw extruder operated at525-550° F. (274-288° C.). The pellets are dried overnight in a vacuumoven and molded into test plaques (2″×2″×0125″) using an injectionmolder operated at 525-550° F. (274-288° C.). The color of the testplaques are measured, as yellowness index values using ASTM D-1925, onten plaques using a spectrophotometer and the average value reported asseen in the table below. Formulation* Yellowness Index 0.08% Phosphite4.5 0.08% Phosphite plus 0.3% UV absorber BB 7.9 0.08% Phosphite plus0.3% UV absorber P 7.4

[0476] Additives are dry blended with polycarbonate pellets (LEXAN®141-111N, General Electric) using a turbula mixture. The dry blends areextruded and pelletized using a single screw extruder operated at 525°F. (274° C.). The pellets are dried overnight in a vacuum oven andmolded into test plaques (2″×2″×0.125″) using an injection molderoperated at 525-550° F. (274-288° C.). The color of the test plaques asyellowness index values is measured on eight plaques using a colorimeterand the average value reported below. Formulation* Yellowness IndexUnstabilized control 6.8 0.3% UV absorber P 8.2 0.3% UV absorber J 7.50.3% UB absorber GG 13.0 0.3% alkylsulfonyl benzotriazole 24.2

EXAMPLE 77

[0477] To ascertain the effect on thermal durability and loss rate froma high solids thermoset acrylic coating of various 2H-benzotriazole UVabsorbers substituted by a variety of electron withdrawing and electrondonating groups, the following tests are carried out.

[0478] A high solids thermoset acrylic clear coat is prepared by mixingan experimental acrylic polyol resin and hexamethoxymethylmelamine(Resimene® 747, Monsanto) at a solids ratio of 60/40. The dodecylbenzenesulfonic acid catalyst (Nacure® 5225; King Industries) is added at 0.70%by weight. A flow aid Modaflow® (Monsanto) is added at 0.25% by weightto form a model acrylic melamine resin system.

[0479] The model clear coat is reduced with xylene to a viscosity of26-27 second using a Zahn #2 cup and applied via a conventional airspray at 50 psi (3.5 Kg/cm²) over a 1″×3″ (2.54 cm×7.62 cm) quartzslide. Cure is achieved by baking the slide for 30 minutes at 260° F.(127° C.). The clear coat is stabilized with 1% by weight of a hinderedamine light stabilizer,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, (TINUVIN®123, Ciba-Geigy). The various test benzotriazole UV absorbers areincorporated at the 5 mmol % by weight in the clear coat. The filmthickness on the quartz slides range from 1.15 to 1.41 mils (0.029 to0.036 mm).

[0480] The films on the quartz slides are weathered according to thefollowing conditions in Xenon Arc Weather-Ometer with a controlledirradiance at 6500 W, using inner quartz and outer borosilicate S-typefilter. The irradiation cycle is as follows: 40 minutes of straightirradiation with no water spray, followed by 20 minutes of light plusfront spray, followed by 60 minutes of light irradiation and finally by60 minutes dart plus rear spray (condensation). The setting is at 0.55W/M² at 340 nm, 1.98 kJ/hour. In the light cycle the black paneltemperature is controlled at 70±2° C. The relative humidity in the lightcycle is in the range of 50-55% and in the dark cycle 100%. Theabsorbance of the long wavelength UV band as a function of Xenon arcweathering hours are recorded in the table below.

[0481] To follow the loss of UV absorbers from the clear coats, UVspectra are measured initially and after weathering at regular timeintervals. The UV spectrophotometer measures absorbance linearly up to5.5 absorbance units using a reference beam attenuation technique.

[0482] It is assumed that the degradation products from the UV absorberdo not contribute to the UV spectrum. This is tested by following theratio of absorbance of the band at about 300 nm and the band at about340 nm. The ratio does not change upon weathering the sample, Thissuggests that the UV spectrum of the weathered films correspond to theamount of UV absorber remaining in the film with very little if anycontribution to the spectrum by photo degradants.

[0483] The data in the table below are based on formula A after 1211hours of exposure of the clear coats containing the test benzotriazoleUV absorbers. Units Com- Absorbance pound Loss G₂ E₁ E₂* A 1.7982hydrogen —PO(OEt)₂ tert-octyl B 1.6300 hydrogen nitro tert-octyl C1.4863 phenyl-S— tert-butyl group I D 1.4002 hydrogen hydrogen group IIE 1.1872 methoxy tert-butyl methyl F 0.5259 hydrogen tert-butyl group IIG 0.4527 hydrogen hydrogen α-cumyl H 0.4420 hydrogen tert-butyl group II 0.4299 hydrogen tert-octyl α-cumyl J 0.4134 hydrogen hydrogentert-octyl K 0.3777 hydrogen tert-octyl tert-octyl L 0.3712 hydrogentert-butyl CH₂CH₂CH₂OH M 0.3433 hydrogen α-cumyl group II N 0.3098 cyanotert-butyl tert-butyl O 0.2689 phenyl-SO₂— tert-butyl group I P 0.2576hydrogen α-cumyl α-cumyl Q 0.2492 hydrogen α-cumyl tert-octyl

[0484] Inspection of these data leads to some clear conclusions aboutthe photostability of 2H-benzotriazole UV absorbers and about the natureof the substitution which will affect that photostability.

[0485] Increased photostability occurs when E₁ is α-cumyl or phenyl andwhen G₂ is an electron withdrawing group such as phenyl-sulfonyl orcyano.

[0486] The nature of the E₂ group has less influence on thephotostability of the benzotriazole UV absorbers.

[0487] From these observations, then an idealized benzotriazole UVabsorber might theoretically be designed where G₂ is an electronwithdrawing group, E₁ is an effective bulky group, and E₂ is a thermallystable moiety. One such idealized compound might be a benzotriazolewhere G₂ is phenylsulfonyl, E₁ is α-cumyl and E₂ is tert-octyl. Thisbenzotriazole is generically claimed in U.S. Pat. No. 5,280,124. Thedata given in Example 78 below confirms this prediction and this“idealized” compound does indeed exhibit a very low loss rate well belowthe present state of the art.

EXAMPLE 78

[0488] This example demonstrates the superior durability ofbenzotriazoles substituted at the 5-position of the benzo ring.

[0489] Following the general procedure of Example 77, a number ofadditional benzotriazole test compounds are incorporated into a highsolids thermoset acrylic melamine resin at such concentrations between1.93 and 3% by weight to give equal molar concentrations of testbenzotriazole in equal film thickness, and sufficient to give a startingabsorbance of approximately 2.0 absorbance units.

[0490] The test discs are exposed in a Xenon-Arc Weather-Ometer at X180cycle (0.45 Watts/M²). The initial UV absorbance is measured followed bymeasurements at roughly 250 hour intervals for the first 2000 hours andevery 500 hours thereafter. Each clear coat also contains 1% by weightof a hindered amine light stabilizer,bis-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, as well.

[0491] The data in the table below are based on compounds of formula Aafter 1253 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ E₁ E₂ R0.2424 hydrogen phenyl α-cumyl Q 0.2351 hydrogen α-cumyl tert-octyl S0.1271 CF₃ α-cumyl tert-octyl T 0.1827 phenyl-SO₂ tert-butyl tert-butyl

[0492] The data in the table below are based on compounds of formula Aafter 1489 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ E₁ E₂ R0.3724 hydrogen phenyl α-cumyl Q 0.287 hydrogen α-cumyl tert-octyl S0.1547 CF₃ α-cumyl tert-octyl T 0.2654 phenyl-SO₂ tert-butyl tert-butyl

[0493] The data in the table below are based on compounds of formula Aafter 2521 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ E₁ E₂ R0.4824 hydrogen phenyl α-cumyl Q 0.4054 hydrogen α-cumyl tert-octyl S0.2192 CF₃ α-cumyl tert-octyl T 0.3570 phenyl-SO₂ tert-butyl tert-butyl

[0494] It is clear from the three tables above that Compounds S andespecially T which have an electron withdrawing group at the 5-positionof the benzo ring are significantly more durable than benzotriazoleswhich do not have such a group on the benzo ring.

[0495] The data in the table below are based on compounds of formula Aafter 1264 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ E₁ E₂ Q0.2293 hydrogen α-cumyl tert-octyl S 0.0921 CF₃ α-cumyl tert-octyl T0.1965 phenyl-SO₂ tert-butyl tert-butyl U 0.0944 phenyl-SO₂ α-cumyltert-octyl V 0.1719 chloro α-cumyl tert-octyl W 0.1655 fluoro α-cumyltert-octyl X 0.1796 hydrogen phenyl tert-octyl

[0496] The data in the table below are based on compounds of formula Aafter 1518 hours of exposure of the clear coats containing the testbenzotriazole UV absorbers. Units Absorbance Compound Loss G₂ E₁ E₂ Q0.2662 hydrogen α-cumyl tert-octyl S 0.1116 CF₃ α-cumyl tert-octyl T0.2423 phenyl-SO₂ tert-butyl tert-butyl U 0.1114 phenyl-SO₂ α-cumyltert-octyl V 0.1955 chloro α-cumyl tert-octyl W 0.1668 fluoro α-cumyltert-octyl X 0.2220 hydrogen phenyl tert-octyl

[0497] The data in these tables clearly show that benzotriazolessubstituted by an electron withdrawing group on the benzo ring,particularly a group such as trifluoromethyl, fluoro or phenylsulfonyl,are especially durable as measured by low loss rate absorbance valuesafter exposure to actinic radiation. Compounds S, U, V and W areespecially durable and fit the profile proposed above. Indeed, theprediction that Compound U would be particularly durable is borne out bythe data above. Inspection of the data for compounds T and U shows theadded beneficial effect of having an effective bulky group such asα-cumyl at the R₁ position compared to a mere alkyl moiety such astert-butyl at that position.

EXAMPLE 79

[0498] This example demonstrates the lack of durability of arepresentative benzotriazole substituted by an electron donating groupon the phenoxy ring relevant to a commercial benzotriazole in a coatingcomposition.

[0499] Following the general procedure of Example 77, representativebenzotriazole test compounds are incorporated into a high solidsthermoset acrylic melamine resin at concentrations between 1.93 and 3%by weight to give equal molar concentrations of the test benzotriazolein equal film thickness and sufficient to give a starting absorbance ofapproximately 2.0 absorbance units. The test samples are exposed asdescribed in Example 77 for 1002 hours. Compound* Units of AbsorbanceLoss Q 0.28 Z 1.58

[0500] It is clear that the presence of an electron donating group onthe phenoxy ring of the benzotriazole adversely affects the durabilityof said benzotriazole.

EXAMPLE 80

[0501] The durability of representative benzotriazoles in thermoplasticsubstrates is determined by incorporating various test compounds intosolvent cast films of poly(vinyl chloride), polycarbonate andpolystyrene resins. The free standing films are mounted into cardboardholders, secured in metal frames and exposed in an Atlas C165 Xenon-arcWeather-Ometer under dry conditions according to ASTM G26 for 1100 and2200 hour exposure. Loss of UV absorber is determined by monitoring theloss of diagnostic UV absorption as described earlier. Performance ismeasured by a change in color or the physical integrity of the film.

[0502] Polycarbonate flake (LEXAN® 145, General Electric) is dissolvedin methylene chloride at room temperature along with between 1 and 3% byweight of test benzotriazole, based on the polycarbonate. Films are castusing a calibrated drawdown bar to prepare 1 mil thick film afterdrying.

[0503] The following test data show the increase in durability obtainedwith a benzotriazole substituted on the 5-position of the benzo ringwith an alkylsulfonyl moiety. These results mirror those obtained withcoating results. Compound* Absorbance (max) (wt %) 0 hrs 1100 hrs Lossunits % Loss AA (2.5) 1.333 1.300 0.033 2.5 (364 nm) P (1.5) 1.062 0.9190.143 13.5 (347 nm) P (2.5) 2.104 1.844 0.260 12.3

EXAMPLE 81

[0504] Following the procedure of Example 80, this example shows theincrease in polycarbonate film of the durability of a benzotriazolesubstituted on the benzo ring with a trifluoromethyl moiety in the5-position after exposure for 2000 hours in the Atlas C165Weather-meter. Compound* Absorbance (max) (wt %) 0 hrs 2000 hrs Lossunits % Loss BB (2.19) 2.654 2.638 0.016 0.6 (352 nm) J (1.81) 2.4542.270 0.184 7.5 (344 nm)

EXAMPLE 82

[0505] The data in the following example show the change in color of thepolycarbonate films exposed according to the procedure of Example 81 asmeasured on an ACS spectro-photometer, large area view, spectralcomponent included d/8, 10° observer, with yellowness index measuredaccording to ASTM D1925 after 2000 hours exposure.

[0506] These data correlates with the advantages seen for the instantcompound in terms of stability and spectral coverage leading to a directincrease in performance of the polycarbonate resin films. Compound* (wt%) Δ Yellowness Index BB (2.19) 2.9 J (1.81) 4.0

[0507] The test compound BB is discernibly less colored than the priorart compound J.

EXAMPLE 83

[0508] The following example shows that the stability increases observedfor benzotriazoles bearing an electron withdrawing group in the5-position of the benzo ring in polar coatings such as thermoset acrylicmelamine resins and polycarbonate are also seen in less polar substratessuch as poly(vinyl chloride) (PVC).

[0509] PVC films of GEON® 27 (Geon Co.) are solvent cast as describedabove with warm tetrahydrofuran (THF) and exposed in an Atlas C165Weather-Ometer as described in Example 60 for 1100 hours. Compound*Absorbance (max) (wt %) 0 hrs 1100 hrs Loss units % Loss AA (2.5) 1.1491.103 0.036 3.1 (368 nm) P (1.5) 1.145 1.022 0.123 10.7 (347 nm) P (2.5)2.211 2.081 0.130 5.6

EXAMPLE 84

[0510] The following example shows an improvement in color protection ofa pigmented polyacetal formulation for a benzotriazole substituted onthe 5-position of the benzo ring with a trifluoromethyl moiety.

[0511] The test additives are dry blended with polyacetal pellets(DELRIN® 500P NC010, DuPont) using a Turbula mixer. The dry blend isextruded and pelletized using a twin screw extruder at a melttemperature of about 410° F. (210° C.). The pellets are molded into testplaques (2″×2″×0.060″) using an injection molder operated at 410-420° F.(204-216° C.). The plaques are exposed in a Xenon-arc Weather-Ometeraccording to automotive test procedure SAE J1885. Exposure is measuredin terms of the total irradiation, measured in kilojoules per squaremeter (kj/m²). Color change in the exposed samples is determined bymeasuring the color of the exposed samples compared to the unexposedsamples as color difference (AE) according to ASTM D2244. The contentsare in weight %. Control Test Sample Contents* Polyacetal 98.8% 98.8%Pigment (CHROMOPHTAL ® Red G) 0.30% 0.30% Hindered Amine 0.25% 0.25%Benzotriazole P 0.60% — Benzotriazole S — 0.60% ACRAWAX C 0.05% 0.05%Color Difference (ΔE) after 600 kJ/m² 6.8 5.8 after 900 kJ/m² 11.7 10.0after 1240 kJ/m² 22.5 20.0

EXAMPLE 85

[0512] The following examples illustrates the superior performance of abenzotriazole substituted on the 5-position of the benzo ring with atrifluoromethyl group in protecting poly(butylene terephthalate) asmeasured by gloss retention.

[0513] The test additives are dry blended with poly(butyleneterephthalate) pellets (VALOX® 315-1001, General Electric) using aTurbula mixer. The dry blends are extruded and pelletized using a twinscrew extruder at 465-490° C. The pellets are molded into test plaques(2″×2″×0.060″) using an injection molder operated at 475-515° F.(246-268° C.). The plaques are exposed in a Xenon arc Weather-Ometeraccording to ASTM G26 test method A. Gloss is measure at 60° on theunexposed and exposed samples using a glossmeter according to ASTM D523.Gloss retention %=(gloss exposed sample/gloss of unexposed sample)×100.The contents are in weight %. Control Test Sample Contents*Poly(butylene 98.35% 98.35% terephthalate) Titanium Dioxide 1.00% 1.00%Hindered Phenol 0.05% 0.05% Phosphite 0.10% 0.10% Benzotriazole P 0.50%— Benzotriazole S — 0.60% Gloss Retention % after 500 hrs exposure   89%  94% after 750 hrs exposure   65%   82%

EXAMPLE 86

[0514] Polystyrene films (crystalline polystyrene obtained from Chevron,free of zinc stearate and mineral oil) are solvent case from solutionsin methylene chloride. These films are exposed to UV light as describedin Example 80. The samples contain no hindered amine stabilizer and aremonitored for color change after 1000 hours exposure, for loss of UVabsorber and for physical integrity (cracking or catastrophic filmfailure). Exposure is stopped after 1500 hours. Exposure 1000 hours and1500 hours Compound* (wt %) Yellowness Index Film Integrity Compound of6.2 film intact Example 31 (2.19%) Compound A 6.9 film failed Compound P9.2 film cracking

[0515] Products from the polystyrene degradation absorbed in theultraviolet obscuring attempts at UV absorber measurements. Color dataobtained after 1000 hours exposure show the effectiveness of the instantcompound of Example 31. After 1500 hours exposure, the films containingcompounds A and P show significant film degradation while the filmcontaining the instant compound of Example 31 is still intact.

EXAMPLE 87

[0516] Polycarbonate films of about 1 mil thickness and containing a UVabsorber are prepared by dissolving polycarbonate granules (LEXAN® 145,General Electric) and UV absorbers in methylene chloride and casting thefilms on a glass plate using a drawdown bar. The films are exposed for2000 hours in a Xenon Arc Weather-O-meter according to ASTM G26 testmethod C and the color change (ΔYI) versus that for unexposed films arerecorded. Sample* (5% by weight) ΔYI Compound B 6.0 Compound of Example43 4.4

[0517] The instant compound provides discernibly better color to thepolycarbonate composition than Compound B.

EXAMPLE 885-Trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole

[0518] When using the general procedure of Example 1 the2-α-cumyl-4-tert-octylphenol is replaced by2-α-cumyl-4-(2-hydroxyethyl)phenol, the title compound is prepared.

What is claimed is:
 1. A compound of formula I, II, III or IV

wherein G₁ is hydrogen or chloro, G₂ is cyano, perfluoroalkyl of 1 to 12carbon atoms, fluoro, —CO—G₃, —COOG₃, —CONHG₃, —CON(G₃)₂, E₃SO— orE₃SO_(2—,) G₃ is hydrogen, straight or branched chain alkyl of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, G₆ is perfluoroalkylof 1 to 12 carbon atoms, G₇ is hydrogen or perfluoroalkyl of 1 to 12carbon atoms, E₁ is hydrogen, straight or branched chain alkyl of 1 to24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1to 24 carbon atoms substituted by one or two hydroxy groups, E₂ and E₂′are independently straight or branched alkyl chain of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by one to three alkyl of 1 to 4 carbon atoms; or E₂ and E₂′ areindependently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to18 carbon atoms substituted by one or more —OH, —OCOE₁₁, —OE₄, —NCO,—NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylor said alkenyl interrupted by one or more —O—, —NH— or —NE₄— groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, —OE₄ or —NH₂ groups or mixtures thereof; n is 1 or 2, when nis 1, E₅ is Cl, OE₆ or NE₇E₈, or E₅ is —PO(OE₁₂)₂, —OSi(E₁₁)₃ or—OCO—E₁₁, or straight or branched chain C₁-C₂₄alkyl which is interruptedby —O—, —S— or —NE₁₁ and which can be unsubstituted or substituted by—OH or —OCO—E₁₁, C₅-C₁₂ cycloalkyl which is unsubstituted or substitutedby —OH, straight chain or branched C₂-C₁₈alkenyl which is unsubstitutedor substituted by —OH, C₇-C₁₅aralkyl, —CH₂—CHOH—E₁₃ or glycidyl, E₆ ishydrogen, straight or branched chain C₁-C₂₄alkyl which is unsubstitutedor substituted by one or more OH, OE₄ or NH₂ groups, or —OE₆ is—(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1 to 12 and E₂₁ isalkyl of 1 to 12 carbon atoms, E₇ and E₈ are independently hydrogen,alkyl of 1 to 18 carbon atoms, straight or branched chain C₃-C₁₈alkylwhich is interrupted by —O—, —S— or —NE₁₁—, C₅-C₁₂cycloalkyl, C₆-C₁₄arylor C₁-C₃hydroxylalkyl, or E₇ and E₈ together with the N atom are apyrrolidine, piperidine, piperazine or morpholine ring, E₅ is—X—(Z)P—Y—E₁₅ wherein X is —O— or—N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z isC₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to three nitrogenatoms, oxygen atoms or a mixture thereof, or is C₃-C₁₂-alkylene,butenylene, butynylene, cyclohexylene or phenylene, each substituted bya hydroxyl group, m is zero, 1 or 2, p is 1, or p is also zero when Xand Y are —N(E₁₆)— and —N(E₁₇)—, respectively, E₁₅ is a group—CO—C(E₁₈)═C(H)E₁₉ or, when Y is —N(E₁₇)—, forms together with E₁₇ agroup —CO—CH═CH—CO—, wherein E₁₈ is hydrogen or methyl, and E₁₉ ishydrogen, methyl or —CO—X—E₂₀, wherein E₂₀ is hydrogen, C₁-C₁₂-alkyl ora group of the formula

wherein the symbols E₁, G₂, X, Z, m and p have the meanings definedabove, and E₁₆ and E₁₇ independently of one another are hydrogen,C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or iscyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the case whereZ is ethylene, also forms ethylene, when n is 2, E₅ is one of divalentradicals —O—E₉—O— or —N(E₁₁)—E₁₀—N(E₁₁)—, E₉ is C₂-C₈alkylene,C₄-C₈alkenylene, C₄alkynylene, cyclohexylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O— or by—CH₂—CHOH—CH₂—O—E₁₄—O—CH₂—CHOH—CH₂—, E₁₀ being straight or branchedchain C₂-C₁₂alkylene which may be interrupted by —O—, cyclohexylene, or

or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazine ring, E₁₄is straight or branched chain C₂-C₈alkylene, straight or branched chainC₄-C₁₀alkylene which is interrupted by —O—, cycloalkylene, arylene or

where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbonatoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms,3-oxapentamethylene, 3-iminopentamethylene or3-methyliminopentamethylene, E₁₁ is hydrogen, straight or branched chainC₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl, E₁₂ is straight or branched chainC₁-C₁₈alkyl, straight or branched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl,C₆-C₁₆aryl or C₇-C₁₅aralkyl, E₁₃ is H, straight chain or branchedC₁-C₁₈alkyl which is substituted by —PO(OR₁₂)₂, phenyl which isunsubstituted or substituted by OH, C₇-C₁₅aralkyl or —CH₂O E₁₂, E₃ isalkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms,alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms orsaid aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, L is alkylene of 1 to 12 carbon atoms, alkylidene of2 to 12 carbon atoms, benzylidene, p-xylylene,α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene, and T is —SO—,—SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—CO—, —CO—CH₂—CO—, —CO—E-CO—,—COO—E—OCO— or —CO—NG₅—E—NG₅—CO—, where E is alkylene of 2 to 12 carbonatoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted orterminated by cyclohexylene of 8 to 12 carbon atoms; G₅ is G₃ orhydrogen, and with the proviso that when T is —SO—, —SO₂—, —SO—E—SO— or—SO₂—E—SO₂—, E₁ is not hydrogen, straight or branched chain alkyl of 1to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of7 to 15 carbon atoms; or when E₃ is alkyl of 1 to 6 carbon atoms, E₁ isnot hydrogen or phenyl, and the sum of E₁ plus E₂ is equal to or greaterthan 8; and when E₃ is alkyl of 8 to 18 carbon atoms or alkenyl of 2 to24 carbon atoms, E₁ is not hydrogen, straight or branched chain of 1 to24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7to 15 carbon atoms; or when G₂ is cyano, —CO—G₃. —CONHG₃, —CON(G₃)₂ or—COOG₃, then E₁ is phenyl or phenylalkyl of 7 to 15 carbon atoms, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms; or when E₁ is hydrogen, E₂ is not methyl.2. A compound according to claim 1 of formula I

wherein G₁ is hydrogen, G₂ is cyano, CF₃—, fluoro, —CO—G₃ or E₃SO₂—, G3is straight or branched chain alkyl of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms, E₁ is phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms, E₂ is straight or branchedalkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenylof 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkylof 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkylsubstituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms;or E₂ is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18carbon atoms substituted by one or more —OH, —OCOE₁₁, —OE₄, —NCO, —NH₂,—NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ is straight orbranched chain alkyl of 1 to 24 carbon atoms; or said alkyl or saidalkenyl interrupted by one or more —O—, —NH— or —NE₄— groups or mixturesthereof and which can be unsubstituted or substituted by one or more—OH, —OE₄ or —NH₂ groups or mixtures thereof; E₃ is alkyl of 1 to 20carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted byone or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms; or is a compound of formula I wherein, G₁ ishydrogen, G₂ is CF₃—, fluoro or E₃SO₂—, E₁ is hydrogen or straight orbranched alkyl of 4 to 24 carbon atoms, E₂ is as defined above, and E₃is straight or branched chain alkyl of 1 to 7 carbon atoms, with theproviso that the sum of the carbon atoms in E₁ and E₂ is greater than orequal to 8 when G₂ is E₃SO₂.
 3. A compound according to claim 1 offormula IIIA

wherein G₁ is hydrogen, G₂ is is CF₃— or fluoro, E₁ is hydrogen,straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7to 15 carbon atoms, E₅ is —OE₆ or —NE₇E₈, or E₅ is —X—(Z)_(p)—Y—E₁₅wherein X is —O— or —N(E₁₆)—, Y is —O— or —N(E₁₇)—, Z is C₂C₁₂-alkylene,C₄-C₁₂-alkylene interrupted by one to three nitrogen atoms, oxygen atomsor a mixture thereof, or is C₃-C₁₂-alkylene, butenylene, butynylene,cyclohexylene or phenylene, each substituted by a hydroxyl group, m is0, 1, 2 or 3, p is 1, or p is also zero when X and Y are —N(E₁₆)— and—N(E₁₇)—, respectively, E₁₅ is a group —CO—C(E₁₈)═C(H)E₁₉ or, when Y is—N(E₁₇)—, forms together with E₁₇ a group —CO—CH═CH—CO—, wherein E₁₈ ishydrogen or methyl, and E₁₉ is hydrogen, methyl or —CO—X—E₂₀, whereinE₂₀ is hydrogen, C₁-C₁₂-alkyl or a group of the formula.


4. A compound according to claim 1 of formula IV

wherein G₆ is CF₃, G₇ is hydrogen or CF₃, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; and L is alkylene of 1 to 12 carbon atoms,alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene,α,α,α′,α′-tetramethyl-m-xylylene or cycloalkylidene.
 5. A compoundaccording to claim 1 of formula I

wherein G₁ is hydrogen, G₂ is CF₃—, E₁ is phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, E₂ is straight orbranched alkyl chain of 1 to 24 carbon atoms, straight or branched chainalkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or saidphenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4carbon atoms; or E₂ is said alkyl of 1 to 24 carbon atoms or saidalkenyl of 2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁,—NH₂ or —NHCOE₁₁, or mixtures thereof, or said alkyl or said alkenylinterrupted by one or more —O— and which can be unsubstituted orsubstituted by one or more —OH, or is a compound of formula I wherein,G₁ is hydrogen, G₂ is CF₃—, E₁ is hydrogen, straight or branched alkylof 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and E₂is as defined above.
 6. A compound according to claim 1 of formula IIIA

wherein G₁ is hydrogen, G₂ is CF₃—, E₁ is hydrogen, straight or branchedalkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, E₅is —OE₆ or —NE₇E₈ where E₆ is hydrogen, straight or branched chainC₁-C₂₄alkyl which is unsubstituted or substituted by one or more OHgroups, or —OE₆ is —(OCH₂CH₂)_(w)OH or —(OCH₂CH₂)_(w)OE₂₁ where w is 1to 12 and E₂, is alkyl of 1 to 12 carbon atoms, and E₇ and E₈ areindependently hydrogen, alkyl of 1 to 18 carbon atoms, straight orbranched chain C₃-C₁₈alkyl which is interrupted by —O—, —S— or —NE₁₁—,C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈together with the N atom are a pyrrolidine, piperidine, piperazine ormorpholine ring.
 7. A compound according to claim 1 of formula IV

wherein G₆ is CF₃, G₇ is hydrogen or CF₃, E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3alkyl of 1 to 4 carbon atoms; and L is methylene.
 8. A compoundaccording to claim 1 which is (a)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzo-triazole;(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;(c)5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;(d)2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)4-tert-octyl-phenol];(e)methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];(f)3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamicacid; (g) methyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;(h) isooctyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate;(i)5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(j)5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzo-triazole;(k)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;(1)5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzo-triazole;(m)5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;(n)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzo-triazole;(o)5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole;(p)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(q)5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(r)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole;(s)5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;(t)5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;(u)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;(v)5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(w)5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(x)5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole;(y) 5-fluoro-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole; (z)5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumyl-phenyl)-2H-benzotriazole;(aa)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)2H-benzotriazole;and (bb)5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole.9. A composition stabilized against thermal, oxidative or light-induceddegradation which comprises, (a) an organic material subject to thermal,oxidative or light-induced degradation, and (b) an effective stabilizingamount of a compound of formula I, II, III or IV according to claim 1.10. A composition according to claim 9 wherein the organic material is anatural, semi-synthetic or synthetic polymer.
 11. A compositionaccording to claim 10 wherein the polymer is a polyolefin,polycarbonate, a styrenic, ABS, a nylon (polyamide), a polyester, apolyurethane, a polyacrylate, a rubber modified styrenic, poly(vinylchloride), poly(vinyl butyral), polyacetal (polyoxymethylene), or otherblends or copolymers such as poly(ethylene/1,4-cyclohexylenedimethyleneterephthalate) PETG or an ethylene/acrylic acid copolymer or saltsthereof (an ionomer).
 12. A composition according to claim 11 whereinthe polymer is a polyester.
 13. A composition according to claim 12wherein the polyester is poly(ethylene terephthalate), poly(butyleneterephthalate) or poly(ethylene naphthalenedicarboxylate), or copolymerpoly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.
 14. Acomposition according to claim 10 wherein the polymer is a thermoplasticpolymer.
 15. A composition according to claim 11 wherein the polymer isis a polyolefin or polycarbonate.
 16. A composition according to claim15 wherein the polymer is polyethylene or polypropylene.
 17. Acomposition according to claim 16 wherein the polymer is polypropylene.18. A composition according to claim 9 which additionally contains aneffective stabilizing amount of at least one other UV absorber selectedfrom the group consisting the benzotriazoles, the s-triazines,hydroxy-benzophenones, the a-cyanoacrylates, the oxanilides andbenzoates.
 19. A composition according to claim 18 wherein the other2-hydroxyphenyl-2H-benzotriazole is selected from the group consistingof 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole;2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;and2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzo-triazole.20. A composition according to claim 19 wherein the other benzotriazoleis 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;2-[2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; or2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzo-triazole.21. A composition according to claim 9 which also contains an effectivestabilizing amount of a hindered amine.
 22. A composition according toclaim 11 wherein the polymer is a copolymer of ethylene/acrylic acid oran alkali metal, alkaline earth metal or transition metal salt thereof(an ionomer).